CN107863530A - A kind of method that high-density lithium iron phosphate is prepared using siderite - Google Patents

A kind of method that high-density lithium iron phosphate is prepared using siderite Download PDF

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CN107863530A
CN107863530A CN201711070611.3A CN201711070611A CN107863530A CN 107863530 A CN107863530 A CN 107863530A CN 201711070611 A CN201711070611 A CN 201711070611A CN 107863530 A CN107863530 A CN 107863530A
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iron
siderite
lithium
solution
phosphate
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CN107863530B (en
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谷亦杰
秦文娟
陈蕴博
刘成全
王海峰
刘洪权
陈林
王萌
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Shandong University of Science and Technology
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C01B25/375—Phosphates of heavy metals of iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion 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
    • 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

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of method that high-density lithium iron phosphate is prepared using siderite, it is directly added into phosphoric acid in siderite and obtains the solution of iron first, the solution of iron mixes with high-molecular copolymer P (DMDAAC AM), hydrogen peroxide is added in mixed solution and fully reacts to obtain ferric lithium phosphate precursor phosphate dihydrate iron, phosphate dihydrate iron after lithium carbonate and glucose mixed sintering again with obtaining LiFePO4.The raw material that the present invention utilizes is siderite, siderite is a kind of more extensive mineral of distribution, iron ore can be used as to refine iron, presoma phosphate dihydrate iron is directly synthesized with siderite, not only eliminate the power consumption step that iron ore refines iron, the purpose that anode material for lithium-ion batteries directly obtains from nature is realized, and siderite is easier for iron powder and phosphatase reaction, improves the feasibility of reaction.

Description

A kind of method that high-density lithium iron phosphate is prepared using siderite
Technical field
The invention belongs to electrochemical field, the method that the sub- cell positive material of lithium ion is prepared especially with siderite.
Background technology
Lithium ion battery is the remarkable new generation of green high-energy battery of performance, it has also become the emphasis of hi-tech development it One, and the LiFePO4 synthetic method as anode material for lithium-ion batteries is the developing most important thing.Currently with sparring The method of ore deposit synthesizing iron lithium phosphate battery is, first by siderite using addition oxidant and phosphorus after sulfuric acid, hydrochloric acid or nitric acid dissolving Acid or phosphate reaction generation precursor of lithium ionic cell positive material ferric phosphate, ferric phosphate synthesize with lithium carbonate and C sintering again LiFePO4.Such as：
Chinese Patent Application No. 201210591476.8 discloses a kind of lithium ion battery anode material lithium iron phosphate forerunner The preparation method of body, siderite using sulfuric acid or salt Ore Leaching and is first adjusted into solution concentration, then add hydrogen peroxide or ozone Oxidant and precipitating reagent, by controlling synthesis condition to select element beneficial to electrochemical performances of lithium iron phosphate in siderite Property enter precipitation, dry after produce ferric lithium phosphate precursor.
Chinese Patent Application No. 200810031119.3 discloses a kind of comprehensive utilization ilmenite and prepares LiFePO4 forerunner The method of body：By ilmenite Ore Leaching, filter to get filtrate, in a certain amount of other sources of iron of dissolved in filtrate so that mixing is molten Fe concentration is that 0.01-3mol/L, Ti and Fe mol ratio are 0.0005-0.5 in liquid；Appropriate oxygen is added into mixed solution Agent, with the pH=1.5-6.0 of the aqueous solution regulation system of alkali so that part iron and the co-precipitation of some foreign ions, filtering, obtain To filtrate；Precipitating reagent (0.01-6mol/L), and the pH=4.0-14.0 of the aqueous solution regulation system with alkali are added into filtrate, 10min-24h is reacted in 10-90 DEG C of stirred reactor, filtering, washing, will be deposited in after being dried at 50-150 DEG C in air Presoma-doping type metallic element that 1-24h produces lithium ion battery anode material lithium iron phosphate is calcined at middle 300-800 DEG C Di-iron trioxide.
Although LiFePO4 chemical property prepared by the method that above-mentioned two document is recorded is good, following lack also be present Fall into, one is due to need to add the sour iron leaching by siderite, so technical process is grown, combined coefficient is low；Two be due to add Enter sulfuric acid, hydrochloric acid or nitric acid, introduce the impurity element S O for influenceing battery performance4 2-、CL-And NO3 -Deng.
Sulfuric acid, hydrochloric acid or nitric acid are added without at present, directly with molysite, lithium salts and phosphoric acid, synthesizes phosphorus under hydrothermal conditions Sour iron lithium, for example, Chinese Patent Application No. 201110045252.2 disclose one kind increase substantially low-temperature hydrothermal synthesis lithium from Sub- cell positive material LiFePO4Possesses the method for excellent electrochemical performance, it is by lithium salts, molysite and phosphoric acid according to certain Order of addition and proportioning, pulpous state precursor is prepared in water, then adds a certain amount of organic solvent, then in hydro-thermal bar The nanometer LiFePO with excellent chemical property is prepared under part4Positive electrode.The patent raw material uses soluble ferric iron salt, can Producing for dissolubility molysite consumes the substantial amounts of energy, adds reactions steps.
In addition, the capacity of battery is an important indicator for weighing accumulator property, and there are some property in LiFePO4 The defects of can, because the lithium iron phosphate particles of existing synthesis are small, cause tap density very low with compacted density, cause ferric phosphate The energy density of lithium battery is relatively low.
China Patent Publication No. CN104817059A discloses one kind and prepares battery-grade iron phosphate by iron powder and phosphatase reaction Method, it is to mix iron powder with phosphoric acid,diluted, reaction generation Fe (H2PO4)2, then add oxidizing generation ferric phosphate Precipitation, it is filtered, be dried to obtain high-purity battery-grade iron phosphate i.e. Iron phosphate (FePO4) dihydrate；Iron phosphate (FePO4) dihydrate is metastrengite The nano-sheet crystal of (fosfosiderite) crystal formation.The defects of technology of the disclosure is present be：One is due to that main raw material is iron powder, Common knowledge, iron powder are not nature naturally occurrings, are that a kind of regrowth forms, it is necessary to make steel, and steel-making is that a comparison is answered Miscellaneous process, to expend substantial amounts of electric energy, if with a kind of regrowth go synthesis of anode material of lithium-ion battery this certainly not A kind of recommendable good method；Second, generating hydrogen during the course of the reaction, hydrogen is a kind of inflammable and explosive gas, in sky When reaching certain proportion in gas, running into naked light can explode, and this not only brings harmfulness to whole process, also require operation Instrument has very high operative skill.Thus, technology disclosed in the document can not be widely applied and industrialization, also do not met and worked as The policy of preceding energy-conserving and environment-protective.
The content of the invention
In order to overcome the existing technical process for preparing existing for LiFePO4 technology to grow, combined coefficient is low, and danger coefficient height is not Technological deficiency easy to operate and containing impurity element, while in order to improve the density of LiFePO4 so as to improve lithium ion battery Capacity, the present invention provides a kind of method that anode material for lithium-ion batteries is prepared using siderite.
To reach above-mentioned purpose, the present invention adopts the technical scheme that：
A kind of method that high-density lithium ion battery anode material is prepared using siderite, it is characterised in that
The first step：Dissolve siderite
Phosphoric acid is directly added into siderite, it is desirable to which the concentration of phosphoric acid is 0.2-0.3mol/L, it is desirable to iron and pure phosphoric acid Mol ratio is 2:(4-8), reaction temperature are 0-100 DEG C, reaction time 1-5h, after abundant reaction, are filtrated to get the molten of iron Liquid, chemical equation are：
FeCO3+2H3PO4=Fe2++2(H2PO4)-+H2O+CO2
Second step:The solution of iron mixes with high-molecular copolymer P (DMDAAC-AM)
The solution for the iron that the first step is obtained is added among P (DMDAAC-AM) solution and is sufficiently stirred, and makes the two mixing equal It is even, it is desirable to which that the mass ratio of P (DMDAAC-AM) and siderite is 1:10~1:50；
3rd step:The mixed solution of iron and P (DMDAAC-AM) reacts with hydrogen peroxide
Hydrogen peroxide is added in the mixed solution of second step, the concentration of hydrogen peroxide is 5-30wt%, it is desirable to iron and pure dioxygen The mol ratio of water is 2:(1-1.5), reaction temperature are 50-100 DEG C, reaction time 1-5h, after abundant reaction, filter, use Deionized water is washed, is dry that ferric lithium phosphate precursor phosphate dihydrate iron, chemical equation are：
2Fe2++4(H2PO4)-+H2O2+2H2O=2FePO4·2H2O↓+2H3PO4
4th step：By phosphate dihydrate iron prepared by the 3rd step with obtaining ferric phosphate after lithium carbonate and glucose mixed sintering Lithium, lithium phosphate mix mol ratio as 2 with lithium carbonate and glucose (being counted using carbon):(1-1.1):(0.5-0.8), react in protection gas Carried out in atmosphere, reaction temperature is 600-800 DEG C, reaction time 5-15h.
Chemical equation is：
2FePO4·2H2O↓+Li2CO3+ 0.5C=2LiFePO4+1.5CO2+2H2O。
The material ferric lithium phosphate prepared by present invention process is used as positive pole, and graphite is negative pole, makes lithium ion battery.
Illustrate advantages of the present invention below according to reaction mechanism：
1st, the present invention phosphoric acid is directly added in siderite, by control phosphoric acid concentration and with reaction temperature and time, Iron in siderite is leached to obtain the solution of iron, high-molecular copolymer P (DMDAAC-AM) is then added in the solution of iron, Because P (DMDAAC-AM) is the copolymer of dimethyl diallyl ammonium chloride and acrylamide, it is a kind of vitreous solid, Easily water suction, it is important water-soluble polymer, and has flocculability and thickening property concurrently, when in iron and P (DMDAAC-AM) After adding hydrogen peroxide in mixed solution, due to P (DMDAAC-AM) delayed precipitation so that reacted ferric phosphate particle diameter is big, 10um or so is arrived in the lithium iron phosphate particles control finally sintered, and tap density reaches 1.5-2g/cm3, so as to improve phosphoric acid The energy density of lithium iron battery.
2nd, the present invention is by controlling the concentration of phosphoric acid and obtaining LiFePO4 forerunner with reaction temperature and time directly reaction Body phosphate dihydrate iron, reacted phosphate dihydrate iron in phosphoric acid in the form of precipitation exist, directly filtering just obtain it is pure before Body phosphate dihydrate iron is driven, so not only eliminates in advance with the process of iron in hydrochloric acid or sulfuric acid leaching siderite, reduces cost, And other impurity for being unfavorable for battery performance are not introduced, improve the electric conductivity of battery.
3rd, the raw material that the present invention utilizes is siderite, and siderite is a kind of more extensive mineral of distribution, can be used as iron Ore refines iron, directly synthesizes presoma phosphate dihydrate iron with siderite, not only eliminates the power consumption step that iron ore refines iron Suddenly, realize the purpose that anode material for lithium-ion batteries directly obtains from nature, and siderite for iron powder more Easily and phosphatase reaction, the feasibility of reaction is improved.
4th, it is the CO that colorless and odorless is odorless at normal temperatures that the present invention, which adopts the gas generated during the course of the reaction,2Gas, CO2Gas Body does not injure to human body, CO that is easily operated without combustibility, and generating2Play a part of agitating solution, add water chestnut The activity of iron ore, further increase the feasibility of reaction
In a word, the present invention is that a kind of energy consumption is low, safety coefficient is high, is easy to the anode material for lithium-ion batteries for preparing promoted Method.
Brief description of the drawings
Fig. 1 is SEM (SEM) figure of LiFePO4 prepared by embodiments of the invention 1.
Fig. 2 is X-ray powder diffraction (XRD) figure of LiFePO4 prepared by embodiments of the invention 1.
Fig. 3 is SEM (SEM) figure of LiFePO4 prepared by embodiments of the invention 2.
Fig. 4 is X-ray powder diffraction (XRD) figure of LiFePO4 prepared by embodiments of the invention 2.
Technical scheme is further illustrated with reference to instantiation.
Embodiment one is by taking the siderite of the ferric carbonate containing 1mol as an example, and the concentration of phosphoric acid is 0.2mol/L, the concentration of hydrogen peroxide For 10wt%, specific preparation method is：
The first step：Dissolve siderite
It is 2 according to the mol ratio of iron and pure phosphoric acid:7, it is directly added into siderite with H3PO is calculated as 3.5mol phosphoric acid, Now reaction temperature is 40 DEG C, reaction time 5h, after abundant reaction, obtains the solution of iron；
Second step:The solution of iron mixes with P (DMDAAC-AM)
The solution for the iron that the first step is obtained is added among P (DMDAAC-AM) solution and is sufficiently stirred, and makes the two mixing Uniformly, it is desirable to which siderite and P (DMDAAC-AM) mass ratio are 10:1；
3rd step:The solution of iron reacts with hydrogen peroxide
It is 2 according to the mol ratio of iron and pure hydrogen peroxide:1, added in the solution of iron with H2O2It is calculated as 0.5mol dioxygen Water, hydrogen peroxide concentration 10wt%, now reaction temperature is 70 DEG C, reaction time 3h, after abundant reaction, filtering, is spent Ion water washing, dry presoma phosphate dihydrate iron；
4th step：By phosphate dihydrate iron prepared by the first step with obtaining ferric phosphate after lithium carbonate and glucose sugar mixed sintering Lithium, ferric phosphate mix mol ratio as 2 with lithium carbonate and glucose sugared (being counted using carbon):1:0.6, react and carried out in protective atmosphere, this When reaction temperature be 700 DEG C, reaction time 10h.The scanning electron microscope diagram and x-ray powder of the LiFePO4 of preparation spread out Penetrate figure and see Fig. 1-2 respectively.
Lithium iron phosphate particles tap density prepared by embodiment one reaches 1.7g/cm3。
The LiFePO4 prepared using embodiment one is as positive pole, and graphite is negative pole, and it is 3V that can be prepared into cell voltage, 18650 battery capacities are 1300mAh lithium ion battery.
Embodiment two
For embodiment two by taking 1mol siderites (being counted by ferric carbonate) as an example, the concentration of phosphoric acid is 0.3mol/L, hydrogen peroxide it is dense Spend is for 20wt%, specific preparation method：
The first step：Dissolve siderite.
It is 2 according to the mol ratio of iron and pure phosphoric acid:4, it is directly added into siderite with H3PO is calculated as 2mol phosphoric acid, phosphorus Acid concentration is 0.3mol/L, and now reaction temperature is 70 DEG C, reaction time 3h, after abundant reaction, obtains the solution of iron；
Second step:The solution of iron mixes with P (DMDAAC-AM)
The solution for the iron that the first step is obtained is added among P (DMDAAC-AM) solution and is sufficiently stirred, and makes the two mixing Uniformly, it is desirable to which siderite and P (DMDAAC-AM) mass ratio are 20:1.
3rd step:The solution of iron reacts with hydrogen peroxide.
It is 2 according to the mol ratio of iron and pure hydrogen peroxide:1.5, added in the solution of iron with H2O2It is calculated as the double of 0.75mol Oxygen water, now reaction temperature is 90 DEG C, reaction time 1h, after abundant reaction, filtering, is washed with deionized, is dry Presoma phosphate dihydrate iron；
4th step：By phosphate dihydrate iron prepared by the first step with obtaining ferric phosphate after lithium carbonate and glucose mixed sintering Lithium, ferric phosphate mix mol ratio as 2 with lithium carbonate and glucose (being counted using carbon):1.1:0.6；Reaction is carried out in protective atmosphere, Now reaction temperature is 650 DEG C, reaction time 12h.The scanning electron microscope diagram and x-ray powder of the LiFePO4 of preparation Diffraction pattern is shown in Fig. 3-4 respectively.
Lithium iron phosphate particles tap density prepared by embodiment two reaches 1.75g/cm3。
The LiFePO4 prepared using embodiment two is as positive pole, and graphite is negative pole, and it is 3V that can be prepared into cell voltage, 18650 battery capacities are 1300mAh.

Claims (1)

  1. A kind of 1. method that high-density lithium iron phosphate is prepared using siderite, it is characterised in that
    The first step：Dissolve siderite
    Phosphoric acid is directly added into siderite, it is desirable to which the concentration of phosphoric acid is 0.2-0.3mol/L, it is desirable to mole of iron and pure phosphoric acid Than for 2:(4-8), reaction temperature are 0-100 DEG C, reaction time 1-5h, after abundant reaction, are filtrated to get the solution of iron, change Learning reaction equation is：
    FeCO3+2H3PO4=Fe2++2(H2PO4)-+H2O+CO2
    Second step:The solution of iron mixes with high-molecular copolymer P (DMDAAC-AM)
    The solution for the iron that the first step is obtained is added among P (DMDAAC-AM) solution and is sufficiently stirred, and makes the two well mixed, It is required that the mass ratio of P (DMDAAC-AM) and siderite is 1:10~1:50；
    3rd step:The mixed solution of iron and P (DMDAAC-AM) reacts with hydrogen peroxide
    Hydrogen peroxide is added in the mixed solution of second step, the concentration of hydrogen peroxide is 5-30wt%, it is desirable to iron and pure hydrogen peroxide Mol ratio is 2:(1-1.5), reaction temperature are 50-100 DEG C, reaction time 1-5h, after abundant reaction, filtering, spend from It is sub- water washing, dry that ferric lithium phosphate precursor phosphate dihydrate iron, chemical equation are：
    2Fe2++4(H2PO4)-+H2O2+2H2O=2FePO4·2H2O↓+2H3PO4
    4th step：By phosphate dihydrate iron prepared by the 3rd step with obtaining LiFePO4 after lithium carbonate and glucose mixed sintering, phosphorus Sour lithium mixes mol ratio as 2 with lithium carbonate and glucose (being counted using carbon):(1-1.1):(0.5-0.8), reacts in protective atmosphere Carry out, reaction temperature is 600-800 DEG C, reaction time 5-15h；
    Chemical equation is：
    2FePO4·2H2O↓+Li2CO3+ 0.5C=2LiFePO4+1.5CO2+2H2O。
CN201711070611.3A 2017-11-03 2017-11-03 Method for preparing high-density lithium iron phosphate by adopting siderite Active CN107863530B (en)

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CN108987749A (en) * 2018-08-28 2018-12-11 深圳市德方纳米科技股份有限公司 The method of ferric phosphate, the preparation method of iron manganese phosphate for lithium and lithium iron phosphate positive material are prepared by phosphorus ore
CN114613965A (en) * 2022-03-22 2022-06-10 宜昌邦普循环科技有限公司 Preparation method and application of lithium iron phosphate/carbon composite material
CN114835101A (en) * 2022-05-25 2022-08-02 雅安天蓝新材料科技有限公司 Composition for preparing lithium iron phosphate, preparation method of lithium iron phosphate and battery anode material
CN115477292A (en) * 2022-10-10 2022-12-16 唐山亨坤新能源材料有限公司 Method for preparing iron phosphate from iron ore powder
CN117797764A (en) * 2024-02-28 2024-04-02 广东顺控自华科技有限公司 Calcium-based siderite and preparation method and application thereof
CN117797764B (en) * 2024-02-28 2024-06-07 广东顺控自华科技有限公司 Calcium-based siderite and preparation method and application thereof

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