CN102765707B - Micro-and nanoscale ferric phosphate, its solvent extraction-microemulsion preparation method and application thereof - Google Patents
Micro-and nanoscale ferric phosphate, its solvent extraction-microemulsion preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of inorganic material preparation, specifically to micro-and nanoscale ferric phosphate, its solvent extraction-microemulsion preparation method and an application thereof. The method comprises the following steps of: a, preparing a microemulsion containing Fe<3+>: 1) preparing an aqueous solution of ferric salt and adjusting pH to 1-4; and 2) mixing organic phosphonic (phosphine) acid extractant or organic carboxylic acid extractant and an organic amine extractant to obtain a mixed extractant with the concentration of 0.1-0.5 g/mL; performing mixed extraction on the aqueous solution of ferric salt and the mixed extractant to obtain the microemulsion containing Fe<3+>; b, preparing a PO4<3-> microemulsion: performing a mixed extraction on a phosphoric acid solution and the mixed extractant to obtain the PO4<3-> containing microemulsion; and c, preparing the micro-and nanoscale ferric phosphate: mixing the microemulsion containing Fe<3+> and the microemulsion containing PO4<3->, stirring, reacting to generate a white precipitate, and carrying out solid-liquid separation to obtain the micro-and nanoscale ferric phosphate. The advantage of the method is that the preparation technology is simple, and the product has excellent electrochemical performance.
Description
Technical field
The present invention relates to field of inorganic material preparing technology, particularly, the present invention relates to a kind of preparation method and application that receive microscale tertiary iron phosphate and solvent extraction-microemulsion thereof.
Background technology
Tertiary iron phosphate is because its excellent chemical property has important using value in fields such as lithium secondary battery electrode materials.Owing to receiving the tertiary iron phosphate, particularly nano ferric phosphate of microscale, there is larger specific surface area and activity, can be directly with it as positive electrode material, there is good charge-discharge performance; In addition, can significantly improve its chemical property as another kind of anode material for lithium secondary battery with receiving the synthetic iron lithium phosphate of tertiary iron phosphate of microscale.The inorganic salt material of microscale received adopts hydrothermal method conventionally, and coprecipitation method, microemulsion method and non-aqueous solvent method etc. are synthetic.Wherein microemulsion method is due to the diversity of preparation form, easy and simple to handle, the feature such as granularity is controlled and enjoy people to pay attention to.Microemulsion method is in the time preparing nano particle, conventionally adopt tensio-active agent, general way is exactly by tensio-active agent, and oil and water form microemulsion, and reaction source is dissolved in wherein, under certain condition, nano particle forms in microemulsion system, and tensio-active agent can prevent that on the one hand particle from growing up or reuniting, on the other hand, play sometimes template action, but its shortcoming is that to lose tensio-active agent be cost, and can not scale preparation.In recent years, the report of useful solvent-extracted method synthetic materials.The Shana O.Kelley group of University of Toronto, adopts lauryl amine first metal ion to be transferred to organic phase, then, under reductive agent exists, prepares nano-metal particle or alloy; Changchun should be changed the people such as the Guo Fuqiang of institute and adopt solvent-extracted method to synthesize the fluorochemical of different-shape, as hollow microsphere CaF
2, YF
3nano flower, specifically adopts respectively two kinds of extraction agents loaded metal positively charged ion and hydrofluoric acid respectively, and then two kinds of organic phases containing reaction source are mixed, but these methods all do not relate to the problem of the recycling of extraction agent.Along with the development of nanometer and porous material subject, the synthetic report in succession of the tertiary iron phosphate of various patterns and structure.The Charles Delacourt of France etc., by regulation and control aqueous pH values, strictly control reaction conditions, make the H in water
3pO
4and FeCl
3react, generated the tertiary iron phosphate of micron-sized indefiniteness and crystalline state.Chinese patent 201010209297.4 has been told about a kind of method of preparing tertiary iron phosphate with nonionogenic tenside, specifically under nonionogenic tenside exists, in aqueous phase system, synthesize the tertiary iron phosphate of particle diameter as 50～300nm as phosphorus source and source of iron respectively taking phosphoric acid salt and molysite, be mainly used in the preparation of iron lithium phosphate.Chinese patent 200810026602.9 has been reported a kind of high-density spherical iron phosphate and preparation method thereof, and prepared material is mainly for the preparation of anode material for lithium secondary battery iron lithium phosphate.Specifically using phosphoric acid salt and molysite respectively as phosphorus source and source of iron, in the time being made into the aqueous solution, add respectively neutralizing agent and additive, after reaction, material processing is obtained to 1.5～5 microns of median sizes, tap density>=0.95g/cm
3, particle disperses, high-density spherical iron phosphate of uniform size.
Have multiplely although prepare the method for iron lithium phosphate, to receive the tertiary iron phosphate of microscale as raw material, prepare iron lithium phosphate, also just get more and more people's extensive concerning.At present, receive the tertiary iron phosphate of microscale, its preparation method exists and yields poorly, and cost is high or be that the material particle size of preparation is not little, the problems such as material activity deficiency.
Summary of the invention
The object of the present invention is to provide one to receive microscale tertiary iron phosphate.
The method that a further object of the present invention has been to provide the preparation of solvent extraction-microemulsion method to receive microscale tertiary iron phosphate.
An also object of the present invention has been to provide a kind of application of receiving microscale tertiary iron phosphate.
Receive the method for microscale tertiary iron phosphate according to solvent extraction of the present invention-microemulsion method preparation, said method comprising the steps of:
A preparation contains Fe
3+microemulsion
1) prepare the aqueous solution of molysite, and to regulate pH be 1～4;
2) organo phosphoric extractant or organic phospho acid extraction agent or organic carboxyl acid extraction agent and organic amine extraction agent are mixed, and dilute with thinner, obtain mixed extractant, wherein the concentration of mixed extractant is 0.1～0.5g/mL;
3) by step 1) in the aqueous solution and the step 2 of molysite) in mixed extractant carry out hybrid extraction, static, phase-splitting, gets organic phase, obtains containing Fe
3+microemulsion,
B prepares PO
4 3-microemulsion
By phosphoric acid solution and step 2) in mixed extractant carry out hybrid extraction, static, phase-splitting, gets organic phase, obtains containing PO
4 3-microemulsion,
Microscale tertiary iron phosphate is received in c preparation
To contain Fe
3+microemulsion and contain PO
4 3-microemulsion mix, stir, reaction produces white precipitate, solid-liquid separation, the precipitation obtaining is receives microscale tertiary iron phosphate, the organic phase obtaining, uses respectively pickling and washing, after purification, recycles.
Receive the method for microscale tertiary iron phosphate according to solvent extraction of the present invention-microemulsion method preparation, described step 1) in molysite for being selected from iron(ic) chloride and/or iron nitrate, its concentration is 0.5～1mol/L, in described step b, the concentration of phosphoric acid solution is 1～3mol/L, step 3) in when extraction mixed extractant and the volume ratio of iron salt solutions be 10～1: 1, while extraction in step b, the volume ratio of mixed extractant and phosphoric acid solution is 10～5: 1.
Receive the method for microscale tertiary iron phosphate according to solvent extraction of the present invention-microemulsion method preparation, described step 2) in, organo phosphoric extractant or organic phospho acid extraction agent have the general formula of structural formula I, organic carboxyl acid extraction agent has the general formula of formula II, wherein R is straight or branched alkane, organo phosphoric extractant or organic phospho acid extraction agent are conventional organo phosphoric extractant or organic phospho acid extraction agent, as di(2-ethylhexyl)phosphate (2-ethylhexyl) ester (P204), 2-ethylhexyl phosphoric acid list (2-ethylhexyl) ester (P507), two (2, 4, 4-tri-methyl-amyl) phospho acid (Cyanex272) etc., organic carboxyl acid extraction agent, as secondary octyl phenoxy group substituted acetic acid (CA-12), secondary nonylphenoxyacetic acid (CA-100), oleic acid etc., described organic amine extraction agent has the general formula of formula II I～V, and wherein R is straight or branched alkane, organic amine extraction agent, as secondary carbon primary amine (N1923), didecylamine (DDA), trioctylamine (TOA), trialkylamine (N235) etc., the mixing mol ratio of organo phosphoric extractant or organic phospho acid extraction agent or organic carboxyl acid extraction agent and organic amine extraction agent is 1: 1, described thinner is nonpolar alkane, for being selected from the one in normal heptane, normal hexane and kerosene,
Receive the method for microscale tertiary iron phosphate according to solvent extraction of the present invention-microemulsion method preparation, in described step c, contain Fe
3+microemulsion and contain PO
4 3-the mol ratio of microemulsion be 1: 1～3, reaction times is 1～5 hour, for the precipitation obtaining, organic solvent normal heptane, kerosene, Virahol or acetone wash, and the size of prepared iron phosphate grains is 10～500nm, and pattern can be nano particle or the Mesoporous Spheres in non-hole; If 300～800 DEG C of thermal treatments, can also obtain crystal ferric phosphate.
According to one embodiment of the invention, what method of the present invention was concrete comprises the following steps:
A, be pH=1～4 by the acidity adjustment of iron salt solutions;
B, acid routine organophosphorous extractant or organic carboxyl acid extraction agent and organic amine extraction agent are mixed according to a certain percentage, form mixed extractant;
C, mixed extractant is diluted with thinner, the organic phase concentration being made into is: 10～50g/100mL;
D, get the organic phase that above-mentioned C obtains, with certain volume iron salt solutions extraction equilibrium 30min, leave standstill, obtain the load thing Fe that responds
3+microemulsion A; Equally, get the organic phase that above-mentioned C obtains, with the phosphoric acid solution hybrid extraction balance 30min of certain volume, leave standstill, obtain the load thing PO that responds
4 3-microemulsion B;
E, by microemulsion A and microemulsion B mix and blend according to a certain percentage, the white precipitate of generation adopts centrifugal (9000 turn) to separate, for several times, 70 DEG C of vacuum-dryings, weigh and calculate productive rate and characterize for normal heptane or kerosene or Virahol or washing with acetone.
F, supernatant mother liquor after centrifugal, use respectively pickling and washing, purifies organic phase, and the organic phase after purification is reusable.
The microstage tertiary iron phosphate of receiving of the present invention, its preparation method comprises the following steps:
A preparation contains Fe
3+microemulsion
1) prepare the aqueous solution of molysite, and to regulate pH be 1～4;
2) organo phosphoric extractant or organic phospho acid extraction agent or organic carboxyl acid extraction agent and organic amine extraction agent are mixed, and dilute with thinner, obtain mixed extractant, wherein the concentration of mixed extractant is 0.1～0.5g/mL;
3) by step 1) in the aqueous solution and the step 2 of molysite) in mixed extractant carry out hybrid extraction, static, phase-splitting, gets organic phase, obtains containing Fe
3+microemulsion,
B prepares PO
4 3-microemulsion
By phosphoric acid solution and step 2) in mixed extractant carry out hybrid extraction, static, phase-splitting, gets organic phase, obtains containing PO
4 3-microemulsion,
Microstage tertiary iron phosphate is received in c preparation
To contain Fe
3+microemulsion and contain PO
4 3-microemulsion mix, stir, reaction produce white precipitate, solid-liquid separation; the precipitation obtaining is receives microstage tertiary iron phosphate, and the organic phase obtaining, uses respectively pickling and washing; after purification, recycle, the product yardstick finally obtaining is for receiving microstage, and pattern is particle or Mesoporous Spheres.
The tertiary iron phosphate of microscale that what the present invention prepared receive can be used as positive electrode material, particularly, can be used as the positive electrode material of lithium secondary battery and as the starting material of preparing iron lithium phosphate.
Principle of the present invention is for by adopting above-mentioned organo phosphoric extractant or the organic phospho acid extraction agent or organic carboxyl acid extraction agent and organic amine mentioned as extraction agent, and these extraction agents itself contain non-polar group alkyl chain, polar group-POOH ,-COOH ,-NH
2,-NH-or R
3n, therefore has the character of tensio-active agent, and the organic phase after extraction equilibrium is made up of mixed extractant (tensio-active agent), oil phase (alkanes thinner) and micro-pond, i.e. w/o type microemulsion.Microemulsion is thermodynamic stable system, its micro-pond is one " microreactor ", and this " microreactor " has very large interface, therein can the various compound of solubilising, be extraordinary reacting environment, micro-pool size of emulsion is to be determined by the amount of Solubilization of Water.Therefore, in water core, carry out chemical reaction while preparing ultra-fine grain, because reactant is limited in water core, the grain diameter finally obtaining will be subject to the control of water core size, the micelle micella that extractant molecules forms has the effect of template, and the microtexture of microemulsion will affect the pattern of synthesized material.
The microemulsion that this preparation method relates to, contains reactant Fe
3+and H
3pO
4polar group towards the inside in micro-pond, the non-polar group of extraction agent is along the outside radial distribution in micro-pond, in reaction process, micro-pond is destroyed, reactant is contacted generates tertiary iron phosphate nucleus, due to micro-pool size generally tens between hundreds of nanometers, and surrounded by non-polar solvent, therefore the tertiary iron phosphate of nucleation is difficult for growing up, and can obtain receiving the iron phosphate grains of microscale.The microtexture of concrete size and pattern and microemulsion, as bar-shaped, spherical or lamellar micelle micelle, even the formation of vesica etc. is directly related, specifically, relevant with Macroscopic Process such as the treating processess of water content, reaction conditions and the material of the preparation of microemulsion A and B, microemulsion.In this preparation process, thought to form the microemulsion of spherical W/O, both as reactor, again as template contral the pattern of synthetic materials.Because the specific surface energy of nano-particle is high, conventionally at a certain amount of tensio-active agent of its remained on surface, this has also prevented the further reunion of nano-particle.The tertiary iron phosphate of receiving microscale of preparing by present method, the organic content of its remained on surface is below 2%, and particle presents amorphous, and thermal treatment at a certain temperature obtain crystal formation tertiary iron phosphate.
It is that preparation technology is simple that the outstanding advantage of method of tertiary iron phosphate of microscale is received in the preparation that the present invention proposes; Energy consumption is low, can prepare in batches; In system without other additive, relatively good processing, be easy to control; The extraction agent adopting can recycle, and greatly reduces costs; The material property of preparation is stable, as the positive electrode material of lithium secondary battery and the anode material for lithium secondary battery iron lithium phosphate prepared with it, all shows excellent chemical property with it.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram of the prepared tertiary iron phosphate sample of embodiment 1 after Overheating Treatment;
Fig. 2 is transmission electron microscope (TEM) figure of the prepared tertiary iron phosphate sample of embodiment 1;
Fig. 3 is low power transmission electron microscope (TEM) figure of the prepared tertiary iron phosphate sample of embodiment 2;
Fig. 4 is high power transmission electron microscope (TEM) figure of the prepared tertiary iron phosphate sample of embodiment 2.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Be not used in and limit the scope of the invention but these embodiment only limit to the present invention is described.
Embodiment 1
10g mixed extractant (P507 and N1923 mol ratio are 1: 1), be dissolved in 50ml normal heptane, its concentration is 0.2g/mL, water ferric chloride concn is 0.86M, pH is 3, and when extraction, organic phase and water volume ratio are 6: 1, and when extraction starts, the pH of iron salt solutions is 2.5, organic phase load iron concentration is 0.089M, and this is microemulsion A; The concentration of phosphate aqueous solution is 1.75M, and when extraction, organic phase and phosphoric acid water phase volume ratio are 6: 1, and when extraction equilibrium, the concentration of organic phase load phosphoric acid is 0.145M, and this is microemulsion B; Get 5ml A and 3ml B mix and blend, the mol ratio of iron ion and phosphate radical is 1: 1, and the reaction times is 3h, acetone and water washing for precipitation, it is amorphous that productive rate is that 86%, XRD is characterized by, tem analysis particle diameter is 8～10nm, and after the thermal treatment of certain temperature, XRD is characterized by crystalline form.
Adopt the sample making simulated battery of the tertiary iron phosphate of above-mentioned preparation.According to mass ratio FePO
4: acetylene black: PTFE binding agent=80%: be at normal temperatures and pressures mixed to form thin slice at 15%: 5%, be evenly pressed on the substrate taking aluminium net as collector and make electrode slice, as the positive pole of simulated battery.The negative pole of simulated battery uses metal lithium sheet, the LiPF that electrolytic solution is 1mol
6be dissolved in (volume ratio 1: 1) in the EC of 1L and the mixed solvent of DMC.Positive pole, negative pole, electrolytic solution are assembled into simulated battery in the glove box of argon shield.Simulated battery discharges and recharges between 2～4.5V at the electric current of C/20, and obtained capacity is 168mAh/g.
Embodiment 2
5g mixed extractant (oleic acid and N1923 mol ratio are 1: 1), is dissolved in 25ml normal heptane, and its concentration is 0.2g/mL.Water iron nitrate concentration is 0.945M, and pH is 4, and when extraction, organic phase and water volume ratio are 10: 1, and when extraction starts, the pH of iron salt solutions is 3.8, and organic phase load iron concentration is 0.074M, and this is microemulsion A; The concentration of phosphate aqueous solution is 3.01M, and when extraction, organic phase and phosphoric acid water phase volume ratio are 10: 1, and when extraction equilibrium, the concentration of organic phase load phosphoric acid is 0.25M, and this is microemulsion B; Get 32ml A and 18ml B mix and blend, the mol ratio of iron ion and phosphate radical is 1: 2, and the reaction times is 5h, precipitation washing with acetone, XRD is characterized by amorphous, and productive rate is 83%, after the thermal treatment of certain temperature, XRD is characterized by crystalline form, and tem analysis median size is 100nm.
The tertiary iron phosphate that adopts above-mentioned preparation is raw material, takes FePO at 1: 0.5 according to mol ratio
4and Li
2cO
3, after mixing, this mixture is mixed with a certain amount of sucrose again, at high-purity Ar gas or N
2under the protective atmosphere of gas, heat-treat, thermal treatment temp is 650 DEG C, this temperature constant temperature 5 hours, then naturally cools to room temperature, obtains the LiFePO that contains carbon
4matrix material is black powder after grinding.
By sample making simulated battery.According to mass ratio LiFePO
4: acetylene black: PVdF binding agent=85%: be at normal temperatures and pressures mixed to form slurry at 10%: 5%, be evenly coated on the substrate that aluminium foil is collector and make electrode slice, the film thickness of gained is 5-30 micron, as the positive pole of simulated battery.The negative pole of simulated battery uses metal lithium sheet, the LiPF that electrolytic solution is 1mol
6be dissolved in (volume ratio 1: 1) in the EC of 1L and the mixed solvent of DEC.Positive pole, negative pole, electrolytic solution are assembled into simulated battery in the glove box of argon shield.Simulated battery discharges and recharges between 2～4.2V at the electric current of C/2, and obtained capacity is 162mAh/g.
Embodiment 3
10g mixed extractant (Cyanex272 and N235 mol ratio are 1: 1), is dissolved in 20ml normal heptane, and its concentration is 0.5g/mL.Water ferric chloride concn is 0.15M, and pH is 2.4, and when extraction, organic phase and water volume ratio are 1: 1, and when extraction starts, the pH of iron salt solutions is 4.0, and organic phase load iron concentration is 0.11M, and this is microemulsion A; The concentration of phosphate aqueous solution is 3.01M, and when extraction, organic phase and phosphoric acid water phase volume ratio are 5: 1, and when extraction equilibrium, the concentration of organic phase load phosphoric acid is 0.18M, and this is microemulsion B; Get 19ml A and 33ml B mix and blend, the mol ratio of iron ion and phosphate radical is 0.35: 1, and the reaction times is 4.5h, precipitation washing with acetone, XRD is characterized by amorphous, and productive rate is 81%, after the thermal treatment of certain temperature, XRD is characterized by crystalline form, and tem analysis particle diameter is 340nm.
Embodiment 4
10g mixed extractant (CA-12 and DDA mol ratio are 1: 1), is dissolved in 88ml normal hexane, and its concentration is 0.11g/mL.Water iron nitrate concentration is 0.945M, and pH is 1, and when extraction, organic phase and water volume ratio are 10: 1, and when extraction starts, the pH of iron salt solutions is 3.0, and organic phase load iron concentration is 0.054M, and this is microemulsion A; The concentration of phosphate aqueous solution is 1.54M, and when extraction, organic phase and phosphoric acid water phase volume ratio are 8: 1, and when extraction equilibrium, the concentration of organic phase load phosphoric acid is 0.12M, and this is microemulsion B; Get 100ml A and 40ml B mix and blend, the mol ratio of iron ion and phosphate radical is 1.1: 1, and the reaction times is 2.5h, precipitation washed with isopropyl alcohol, XRD is characterized by amorphous, and productive rate is 76%, after the thermal treatment of certain temperature, XRD is characterized by crystalline form, and tem analysis particle diameter is 180nm.
Embodiment 5
In embodiment 1, the mother liquor obtaining after centrifugal, uses respectively pickling and washing, the mixed extractant after being purified.Get this mixed extractant 5g, be dissolved in 25ml normal heptane, its concentration is 0.2g/mL.Water iron nitrate concentration is 0.945M, and pH is 1.5, and when extraction, organic phase and water volume ratio are 6: 1, and when extraction starts, the pH of iron salt solutions is 3.0, and organic phase load iron concentration is 0.069M, and this is microemulsion A; The concentration of phosphate aqueous solution is 3.01M, and when extraction, organic phase and phosphoric acid water phase volume ratio are 6: 1, and when extraction equilibrium, the concentration of organic phase load phosphoric acid is 0.15M, and this is microemulsion B; Get 32ml A and 25ml B mix and blend, the mol ratio of iron ion and phosphate radical is 0.58: 1, and the reaction times is 3.5h, normal heptane washing for precipitation, XRD is characterized by amorphous, and productive rate is 79%, after the thermal treatment of certain temperature, XRD is characterized by crystalline form, and tem analysis particle diameter is 220nm.In addition, the present inventor has also investigated other different types of organo phosphoric extractants or organic phospho acid extraction agent and organic amine extraction agent, and both mol ratios are 1: 1, and other test conditions is with embodiment 1, and result is as shown in table 1.
Product performance and effect prepared by the organo phosphoric extractant of the different kind of table 1 or organic phospho acid extraction agent and organic amine extraction agent
Comparative example 1
For comparative study, we have carried out Electrochemical Properties to commercial phosphoric acid iron, and commercial phosphoric acid iron sample is made to simulated battery.According to mass ratio FePO
4: acetylene black: PTFE binding agent=80%: be at normal temperatures and pressures mixed to form thin slice at 15%: 5%, be evenly pressed on the substrate taking aluminium net as collector and make electrode slice, as the positive pole of simulated battery.The negative pole of simulated battery uses metal lithium sheet, the LiPF that electrolytic solution is 1mol
6be dissolved in (volume ratio 1: 1) in the EC of 1L and the mixed solvent of DMC.Positive pole, negative pole, electrolytic solution are assembled into simulated battery in the glove box of argon shield.Simulated battery discharges and recharges between 2～4.5V at the electric current of C/20, and obtained capacity is 110mAh/g.The result of contrast table 1 can find out, compared with commercial phosphoric acid iron sample, adopts nanometer prepared by this solvent extraction-microemulsion method or the mesoporous microscale tertiary iron phosphate sample of receiving to show good chemical property, and its lithium storage content has obtained large increase.
Comparative example 2
For comparative study, we have selected commercial phosphoric acid iron is simultaneously raw material, takes FePO at 1: 0.5 according to mol ratio
4and Li
2cO
3, after mixing, this mixture is mixed with a certain amount of sucrose again, at high-purity Ar gas or N
2under the protective atmosphere of gas, heat-treat, thermal treatment temp is 650 DEG C, this temperature constant temperature 5 hours, then naturally cools to room temperature, obtains the LiFePO that contains carbon
4matrix material is black powder after grinding.
By sample making simulated battery.According to mass ratio LiFePO
4: acetylene black: PVdF binding agent=85%: be at normal temperatures and pressures mixed to form slurry at 10%: 5%, be evenly coated on the substrate that aluminium foil is collector and make electrode slice, the film thickness of gained is 5-30 micron, as the positive pole of simulated battery.The negative pole of simulated battery uses metal lithium sheet, the LiPF that electrolytic solution is 1mol
6be dissolved in (volume ratio 1: 1) in the EC of 1L and the mixed solvent of DEC.Positive pole, negative pole, electrolytic solution are assembled into simulated battery in the glove box of argon shield.Simulated battery discharges and recharges between 2～4.2V at the electric current of C/2, and obtained capacity is 128mAh/g.The result of contrast table 1 can find out, adopts nanometer prepared by solvent extraction-microemulsion method or the mesoporous microscale tertiary iron phosphate sample of receiving to prepare LiFePO as raw material
4show higher lithium storage content.
Claims (5)
1. the method for microscale tertiary iron phosphate is received in solvent extraction-microemulsion method preparation, it is characterized in that, said method comprising the steps of:
A preparation contains Fe
3+microemulsion
1) prepare the aqueous solution of molysite, and to regulate pH be 1～4;
2) organo phosphoric extractant, organic phospho acid extraction agent or organic carboxyl acid extraction agent and organic amine extraction agent are mixed, and dilute with thinner, obtain mixed extractant, wherein the concentration of mixed extractant is 0.1～0.5g/mL;
3) by step 1) in the aqueous solution and the step 2 of molysite) in mixed extractant carry out hybrid extraction, leave standstill, phase-splitting, gets organic phase, obtains containing Fe
3+microemulsion;
B prepares PO
4 3-microemulsion
By phosphoric acid solution and step 2) in mixed extractant carry out hybrid extraction, leave standstill, phase-splitting, gets organic phase, obtains containing PO
4 3-microemulsion;
Microscale tertiary iron phosphate is received in c preparation
To contain Fe
3+microemulsion and contain PO
4 3-microemulsion mix, stir, reaction produces white precipitate, solid-liquid separation, the precipitation obtaining is receives microscale tertiary iron phosphate, the nano particle that pattern is non-hole or Mesoporous Spheres, the organic phase obtaining, uses respectively pickling and washing, after purification, recycles.
2. the method for microscale tertiary iron phosphate is received in solvent extraction according to claim 1-microemulsion method preparation, it is characterized in that, described step 1) in molysite be iron(ic) chloride and/or iron nitrate, its concentration is 0.5～1mol/L, in described step b, the concentration of phosphoric acid solution is 1～3mol/L, step 3) in when extraction mixed extractant and the volume ratio of iron salt solutions be 10～1:1, while extraction in step b, the volume ratio of mixed extractant and phosphoric acid solution is 10～5:1.
3. the method for microscale tertiary iron phosphate is received in solvent extraction according to claim 1-microemulsion method preparation, it is characterized in that described step 2) in,
Organo phosphoric extractant or organic phospho acid extraction agent have the general formula of structural formula I, organic carboxyl acid extraction agent has the general formula of formula II, wherein R is straight or branched alkane, organo phosphoric extractant or organic phospho acid extraction agent are di(2-ethylhexyl)phosphate (2-ethylhexyl) ester, 2-ethylhexyl phosphoric acid list (2-ethylhexyl) ester and two (2,4,4-tri-methyl-amyl) one of phospho acid, organic carboxyl acid extraction agent is the one of secondary octyl phenoxy group substituted acetic acid, secondary nonylphenoxyacetic acid and oleic acid;
Described organic amine extraction agent has the general formula of formula II I～V, and wherein R is straight or branched alkane, and organic amine extraction agent is the one in secondary carbon primary amine, didecylamine and trialkylamine;
The mixing mol ratio of organo phosphoric extractant, organic phospho acid extraction agent or organic carboxyl acid extraction agent and organic amine extraction agent is 1:1;
Described thinner is nonpolar alkane or kerosene, and described nonpolar alkane is one or more of normal heptane and normal hexane.
4. the method for microscale tertiary iron phosphate is received in solvent extraction according to claim 3-microemulsion method preparation, it is characterized in that, described trialkylamine is trioctylamine.
5. the method for microscale tertiary iron phosphate is received in solvent extraction according to claim 1-microemulsion method preparation, it is characterized in that, in described step c, contains Fe
3+microemulsion and contain PO
4 3-the mol ratio of microemulsion be 1:1～3, the reaction times is 1～5 hour, for the precipitation obtaining, organic solvent normal heptane, kerosene, Virahol or acetone wash.
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