CN102826616A - Ferric fluoride nano material and preparation method thereof - Google Patents
Ferric fluoride nano material and preparation method thereof Download PDFInfo
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- CN102826616A CN102826616A CN2012103391012A CN201210339101A CN102826616A CN 102826616 A CN102826616 A CN 102826616A CN 2012103391012 A CN2012103391012 A CN 2012103391012A CN 201210339101 A CN201210339101 A CN 201210339101A CN 102826616 A CN102826616 A CN 102826616A
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Abstract
The invention discloses a ferric fluoride nano material and a preparation method thereof. The preparation method comprises the following steps of: dissolving inorganic ferric salt in an alcohol solvent to obtain alcohol solution containing iron; dispersing an inorganic fluorine source into the alcohol solution containing iron and adding the solution into a hydrothermal reaction kettle; carrying out the hydrothermal reaction kettle solution for 1 hour to 7 days at a temperature of 40 to 140 DEG C, naturally cooling, carrying out centrifugal separation, washing by ethanol and carrying out vacuum drying to obtain the ferric fluoride nano material. According to the preparation method of ferric fluoride, a volatile hydrofluoric acid fluorine source does not need to be used as a raw material, low-toxicity fluoride is used as the fluorine source, common ferric salt is used as a ferric source, the FeF3.0.33H2O nano material containing trace moisture is obtained by the simple solvent heat treatment, the preparation process is simple, the yield is high and the obtained material has high crystallinity. The method disclosed by the invention is a novel and practical process route for preparing the ferric fluoride nano material and has high actual application value.
Description
Technical field
The invention belongs to the electrode materials field, specifically, the present invention relates to a kind of three and fluoridize ferrum nano material and preparation method thereof.
Background technology
Existing lithium-ion secondary cell also can't satisfy the requirement to the battery high-energy-density such as electromobile; And the specific storage of electrode materials directly influences the energy density of battery, therefore designs and develops to have the top priority that the high reversible capacity electrode materials is the development lithium-ion secondary cell.Novel reversible chemical switching mechanism positive electrode material---transition metal fluorides because higher output voltage and theoretical specific capacity can be provided, obtains researchist's extensive concern.
From the seventies in last century, existing a large amount of relevant fluorochemicals are as the research work of lithium ion secondary battery anode material.The earliest be reported in 1970, synthesized NiF by Seiger etc.
2And realized the limited reversible cycle (H.N.Seiger of material; A.E.Lyall, R.C.Shair, in Proceedings of the 6thInternational Symposium on Power Sources 2:Res:Develop.Non-Mech.Elec.Power Sources; 1970, p.267).Afterwards, Arai etc. has reported TiF
3, VF
3, FeF
3Also has electrochemical activity (H.Arai, S.Okada, Y.Sakurai and J.Yamaki, J.Power Sources, 1997,68,716.) Deng material.These materials reach 80mAh g at the reversible capacity of the voltage range of 2.0-4.5V
-1, mainly be corresponding to M
3+/ M
2+Reversible chemical reaction between the electron pair.Recently, relevant TiF
3And VF
3The report of material reversible chemical switching mechanism points out that in the voltage range of 0.02-4.3V, these materials can provide the g up to 500-600mAh
-1Reversible capacity.In numerous transition metal, the Fe element has cheap, and reserves are abundant, and advantages of environment protection is one of first-selected element of electrode materials.Therefore, three ferric fluorides become one of preferred material of novel reversible chemical switching mechanism material.There are two kinds of different storage lithium mechanism in three ferric fluorides in the charge and discharge process as positive electrode material the time, in the 2.5-4.5V voltage range, a lithium ion is at FeF
3Reversible embeds/deviates from the crystalline structure, is accompanied by Fe
3+/ Fe
2+Transformation, be typical embedding, take off lithium mechanism, lithium storage content is 237mAh g
-1At the 1.5-2.5V voltage range, ferric fluoride can continue and two lithium ion generation electrochemical reducting reactions, forms Fe nanoparticle and LiF, is the reversible chemical switching mechanism, and lithium storage content is 475mAh g
-1FeF
3The reversible capacity that also exists material as electrode materials is less, problems such as cyclical stability difference.This mainly is because FeF
3The relatively poor and charge and discharge process of electroconductibility in exist institutes such as volumetric expansion to cause.To FeF
3These problems, main improved route is with FeF
3With the compound preparation nano composite material of conducting material, increase the conductivity of material.2003, Amatucci etc. were with FeF
3With carbon material (expanded graphite, carbon black and gac), with Prepared by Ball Milling go out the serial nano matrix material (F.Badway, N.Pereira, F.Cosandey, G.G.Amatucci, J Electrochem.Soc., 2003,150A1209).In the voltage range of 2.0-4.5V, the initial discharge capacity 200mAh g of material
-1, corresponding to Fe
3+/ Fe
2+Redox reaction.Subsequently, to same nano composite material, Amatucci etc. have studied its chemical property at the 1.5-4.5V voltage range, and have reported based on Fe
3+/ Fe
0The reduction reaction of three electronics.In the time of 70 ℃, nano composite material has 500mAh g
-1Reversible capacity.2009, Okada etc. utilized ball milled equally, prepare FeF
3/ carbon composite has been studied the charge-discharge performance (M.Nishijima, I.D.Gocheva, S.Okada, T.Doi, J.-i.Yamaki and T.Nishida, J.Power Sources, 2009,190,558) of material in the 2.0-4.5V voltage range.The result shows that the existence of carbon material has improved the specific conductivity of matrix material and reduced the solubleness of fluorochemical in electrolyte solution.Except carbon material, the investigator also passes through FeF
3Carry out the compound chemical property that nano composite material is improved material that obtains with conductive oxide and sulfide.2009, professor Wang Xianyou of University Of Xiangtan utilized ball milled, prepares FeF
3/ MoS
2, FeF
3/ V
2O
5Nano composite material (W.Wu, X.Wang, X.Wang, S.Yang, X.Liu and Q.Chen, Mater.Lett., 2009,63,1788; W.Wu, Y.Wang, X.Wang, Q.Chen, X.Wang, S.Yang, X.Liu, J.Gao and Z.Yang, J.Alloys Compd., 2009,486,93).The result shows, at the 2.0-4.5V voltage range, with respect to the FeF of pure phase
3Material, the chemical property of matrix material has bigger improvement.Though through carrying out compoundly can improving FeF with electro-conductive material
3Conductivity, and improved FeF to a certain extent
3Reversible capacity and cyclical stability, but its performance reaches actual application level far away, the FeF that particularly uses
3Raw material particle size is bigger, causes the FeF in institute's synthetic nano composite material
3Particle diameter is big and particle size distribution range is wide, and the material structure consistence is relatively poor, and being influences the important factor that material is used.
Prepare FeF at present
3Main method be that red stone or iron(ic)chloride and the effect of exsiccant hydrogen fluoride gas are generated amorphous FeF
3At high temperature fluorine gas and metallic iron or red stone effect are obtained FeF
3Recently there is bibliographical information to utilize the Fe (OH) of new system
3Deposition and hydrofluoric acid effect, unnecessary water and the HF of evaporate to dryness obtains FeF then
3Also have bibliographical information to utilize ionic liquid to prepare FeF as solvent and fluorine source
3But these methods also exist the reaction process consumptive material high, gained FeF
3Particle diameter is bigger, needs shortcomings such as deleterious fluorine source.Therefore, utilize the perhaps nontoxic fluorochemical of low toxicity, synthesize the less FeF of particle diameter through simple method as the fluorine source
3Material has significance for the development that promotes the height ratio capacity lithium-ion secondary cell.
Summary of the invention
Based on this, the present invention is directed to and prepare FeF in the prior art
3The deficiency of material provides a kind of simple FeF
3Preparation of nanomaterials.
A kind of three fluoridize the preparation method of ferrum nano material, may further comprise the steps:
(1) inorganic molysite is dissolved in the alcoholic solvent, obtains ferruginous alcoholic solution, in the said ferruginous alcoholic solution, the concentration of iron ion is 1mM～0.2M;
(2) inorganic fluorine source is distributed to the ferruginous alcoholic solution of step (1) after, solution is transferred in the hydrothermal reaction kettle; The iron ion of said inorganic molysite and NH
4HF
2The mol ratio of fluorion be 1: 2～4: 1;
(3) with hydrothermal reaction kettle in 40～140 ℃ of thermal treatments 1 hour to 7 days, naturally cooling, spinning, washing with alcohol, 40～80 ℃ of following vacuum-dryings promptly get.
Among some embodiment therein, inorganic molysite is Fe (NO described in the step (1)
3)
39H
2O, Fe
2(SO
4)
3Or FeCl
3
Among some embodiment therein, alcoholic solvent is ethanol or propyl alcohol described in the step (1).
Among some embodiment therein, in the said ferruginous alcoholic solution of step (1), the concentration of iron ion is 10mM～0.15M.
Among some embodiment therein, the mol ratio of the fluorion of the iron ion of inorganic molysite and inorganic fluorine source is 1: 2.5～3.5: 1 described in the step (2).
Among some embodiment therein, heat treated temperature is 60-120 ℃ in the step (3), and heat treatment time is 2 hours-3 days.
What the present invention provided also that above-mentioned preparation method prepares three fluoridizes ferrum nano material.
It is raw material that the preparation method of the present invention's three ferric fluorides does not need volatility fluorine source hydrofluoric acid, utilizes the fluorochemical of low toxicity to be the fluorine source, and common molysite is a source of iron, through simple solvent heat treatment, obtains to contain the FeF of minor amount of water
30.33H
2The O nano material, the preparation process is simple, and productive rate is high, and gained material percent crystallinity is high.The inventive method is a kind of novelty that ferrum nano material is fluoridized in preparation three, and practical operational path is of very high actual application value.
Description of drawings
Fig. 1 is the FeF of the embodiment of the invention 1 preparation
30.33H
2The XRD spectra of O nano material;
Fig. 2 is the FeF of the embodiment of the invention 1 preparation
30.33H
2The charging and discharging curve of O nano material.
Embodiment
Specify the present invention below in conjunction with accompanying drawing and specific embodiment.
Embodiment 1 three fluoridizes the preparation method of ferrum nano material
May further comprise the steps:
(1) with 0.1263g Fe (NO
3)
39H
2O is dissolved in the 30mL absolute ethyl alcohol, obtains clarifying ferruginous alcoholic solution, and in this ferruginous alcoholic solution, the concentration of iron ion is 10.4mM;
(2) under agitation condition, with 0.0267g NH
4HF
2Be added in the above-mentioned ferruginous alcoholic solution, become water white solution, solution is transferred in the tetrafluoroethylene reaction kettle that volume is 50mL until system; Said Fe (NO
3)
39H
2O and NH
4HF
2Mol ratio be 1: 1.5 (mol ratio of iron ion and fluorion is 1: 3);
(3) with hydrothermal reaction kettle in 80 ℃ of thermal treatments 4 hours, naturally cooling, spinning, washing with alcohol 3 times, 60 ℃ of following vacuum-drying 10h promptly get FeF
30.33H
2The O nano material.
FeF to embodiment 1 preparation gained
30.33H
2The O nano material has been carried out the sign of some structures and character.Shown in Figure 1 is FeF
30.33H
2The XRD spectra of O nano material, diffraction peaks all among the figure all belong to FeF
30.33H
2The characteristic diffraction peak of O, inclusion-free exists.The diffraction peak illustrative material of wideization is made up of nanoparticle, according to the Scherrer formula (D=K λ/Bcos θ, wherein K is the Scherrer constant, its value is 0.89; D is grain-size (nm); B is an integration halfwidth degree) calculate particle diameter and be approximately the 10-15 nanometer.
As shown in Figure 2, be the charging and discharging curve figure of the nano material of present embodiment, as can beappreciated from fig. 2, the specific discharge capacity of the nano material of present embodiment is 137mAh/g.
Embodiment 2 three fluoridizes the preparation method of ferrum nano material
The preparation method is with embodiment 1, just with Fe (NO
3)
39H
2The consumption of O becomes 0.606g (in the ferruginous alcoholic solution, the concentration of iron ion is 50mM), with NH
4HF
2Consumption become 0.1485g (Fe (NO
3)
39H
2O and NH
4HF
2Mol ratio be 1: 1.5, the mol ratio of iron ion and fluorion is 1: 3), XRD spectra shows same acquisition FeF
30.33H
2The O nano material.Particle diameter is approximately the 10-15 nanometer, and the specific discharge capacity of material is 130mAh/g.
Embodiment 3 three fluoridizes the preparation method of ferrum nano material
The preparation method is with embodiment 1, just with Fe (NO
3)
39H
2The consumption of O becomes 1.212g (in the ferruginous alcoholic solution, the concentration of iron ion is 0.1M), with NH
4HF
2Consumption become 0.297g (Fe (NO
3)
39H
2O and NH
4HF
2Mol ratio be 1: 1.5, the mol ratio of iron ion and fluorion is 1: 3), XRD spectra shows same acquisition FeF
30.33H
2The O nano material.Particle diameter is approximately the 10-15 nanometer, and the specific discharge capacity of material is 122mAh/g.
Embodiment 4 three fluoridizes the preparation method of ferrum nano material
The preparation method is with embodiment 1, just with Fe (NO
3)
39H
2The consumption of O becomes 1.818g (in the ferruginous alcoholic solution, the concentration of iron ion is 0.15M), with NH
4HF
2Consumption become 0.4455g (Fe (NO
3)
39H
2O and NH
4HF
2Mol ratio be 1: 1.5, the mol ratio of iron ion and fluorion is 1: 3), XRD spectra shows same acquisition FeF
30.33H
2The O nano material.Particle diameter is approximately the 10-15 nanometer, and the specific discharge capacity of material is 125mAh/g.
Embodiment 5 three fluoridizes the preparation method of ferrum nano material
The preparation method is with embodiment 1, just with Fe (NO
3)
39H
2The consumption of O becomes 2.424g (in the ferruginous alcoholic solution, the concentration of iron ion is 0.2M), with NH
4HF
2Consumption become 0.594g (Fe (NO
3)
39H
2O and NH
4HF
2Mol ratio be 1: 1.5, the mol ratio of iron ion and fluorion is 1: 3), XRD spectra shows same acquisition FeF
30.33H
2The O nano material.Particle diameter is approximately the 10-15 nanometer, and the specific discharge capacity of material is 115mAh/g.
Embodiment 6 three fluoridizes the preparation method of ferrum nano material
The preparation method is with embodiment 1, just with NH
4HF
2Consumption become 0.0206g (Fe (NO
3)
39H
2O and NH
4HF
2Mol ratio be 1: 1, the mol ratio of iron ion and fluorion is 1: 2), XRD spectra shows same acquisition FeF
30.33H
2The O nano material.Particle diameter is approximately the 10-15 nanometer, and the specific discharge capacity of material is 110mAh/g.
Embodiment 7 three fluoridizes the preparation method of ferrum nano material
The preparation method is with embodiment 1, just with NH
4HF
2Consumption become 0.0258g (Fe (NO
3)
39H
2O and NH
4HF
2Mol ratio be 1: 1.25, the mol ratio of iron ion and fluorion is 1: 2.5), XRD spectra shows same acquisition FeF
30.33H
2The O nano material.Particle diameter is approximately the 10-15 nanometer, and the specific discharge capacity of material is 128mAh/g.
Embodiment 8 three fluoridizes the preparation method of ferrum nano material
The preparation method is with embodiment 1, just with NH
4HF
2Consumption become 0.00295g (Fe (NO
3)
39H
2O and NH
4HF
2Mol ratio be 7: 1, the mol ratio of iron ion and fluorion is 3.5: 1), XRD spectra shows same acquisition FeF
30.33H
2The O nano material.Particle diameter is approximately the 10-15 nanometer, and the specific discharge capacity of material is 122mAh/g.
Embodiment 9 three fluoridizes the preparation method of ferrum nano material
The preparation method is with embodiment 1, just with NH
4HF
2Consumption become 0.00258g (Fe (NO
3)
39H
2O and NH
4HF
2Mol ratio be 8: 1, the mol ratio of iron ion and fluorion is 4: 1), XRD spectra shows same acquisition FeF
30.33H
2The O nano material.Particle diameter is approximately the 10-15 nanometer, and the specific discharge capacity of material is 105mAh/g.
The preparation method just becomes 60 ℃ of thermal treatments 1 hour with step (3) with embodiment 4, and XRD spectra shows same acquisition FeF
30.33H
2The O nano material.Particle diameter is approximately the 10-15 nanometer, and the specific discharge capacity of material is 118mAh/g.
Embodiment 11 3 fluoridizes the preparation method of ferrum nano material
The preparation method just becomes 100 ℃ of thermal treatments 15 hours with step (3) with embodiment 4, and XRD spectra shows same acquisition FeF
30.33H
2The O nano material.Particle diameter is approximately the 10-15 nanometer, and the specific discharge capacity of material is 132mAh/g.
Embodiment 12 3 fluoridizes the preparation method of ferrum nano material
The preparation method just becomes 80 ℃ of thermal treatments 24 hours with step (3) with embodiment 4, and XRD spectra shows same acquisition FeF
30.33H
2The O nano material.Particle diameter is approximately the 10-15 nanometer, and the specific discharge capacity of material is 122mAh/g.
Embodiment 13 3 fluoridizes the preparation method of ferrum nano material
The preparation method just becomes 120 ℃ of thermal treatments 3 days with step (3) with embodiment 4, and XRD spectra shows same acquisition FeF
30.33H
2The O nano material.Particle diameter is approximately the 10-15 nanometer, and the specific discharge capacity of material is 119mAh/g.
Embodiment 14 3 fluoridizes the preparation method of ferrum nano material
The preparation method just becomes 80 ℃ of thermal treatments 6 days with step (3) with embodiment 4, and XRD spectra shows same acquisition FeF
30.33H
2The O nano material.Particle diameter is approximately the 10-15 nanometer, and the specific discharge capacity of material is 108mAh/g.
Embodiment 15 3 fluoridizes the preparation method of ferrum nano material
The preparation method is with embodiment 1, just with the Fe (NO in the step (1)
3)
39H
2O becomes Fe
2(SO
4)
3, XRD spectra shows same acquisition FeF
30.33H
2The O nano material.Particle diameter is approximately the 10-15 nanometer, and the specific discharge capacity of material is 103mAh/g.
Embodiment 16 3 fluoridizes the preparation method of ferrum nano material
The preparation method is with embodiment 1, just with the Fe (NO in the step (1)
3)
39H
2O becomes FeCl
3, XRD spectra shows same acquisition FeF
30.33H
2The O nano material.Particle diameter is approximately the 10-15 nanometer, and the specific discharge capacity of material is 121mAh/g.
The above embodiment has only expressed several kinds of embodiments of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art under the prerequisite that does not break away from the present invention's design, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with accompanying claims.
Claims (7)
1. a preparation method who fluoridizes ferrum nano material is characterized in that, may further comprise the steps:
(1) inorganic molysite is dissolved in the alcoholic solvent, obtains ferruginous alcoholic solution, in the said ferruginous alcoholic solution, the concentration of iron ion is 1mM～0.2M;
(2) with NH
4HF
2After being distributed to the ferruginous alcoholic solution of step (1), solution is transferred in the hydrothermal reaction kettle; The iron ion of said inorganic molysite and NH
4HF
2The mol ratio of fluorion be 1: 2～4: 1;
(3) with hydrothermal reaction kettle in 40～140 ℃ of thermal treatments 1 hour to 7 days, naturally cooling, spinning, washing with alcohol, vacuum-drying promptly gets.
2. as claimed in claim 1 three fluoridize the preparation method of ferrum nano material, it is characterized in that, inorganic molysite is Fe (NO described in the step (1)
3)
39H
2O, Fe
2(SO
4)
3Or FeCl
3
3. as claimed in claim 1 three fluoridize the preparation method of ferrum nano material, it is characterized in that, in the said ferruginous alcoholic solution of step (1), the concentration of iron ion is 10mM-0.15M.
As claim 1-3 each described three fluoridize ferrum nano material the preparation method, it is characterized in that alcoholic solvent is ethanol or propyl alcohol described in the step (1).
5. as claimed in claim 1 three fluoridize the preparation method of ferrum nano material, it is characterized in that the iron ion and the NH of inorganic molysite described in the step (2)
4HF
2The mol ratio of fluorion be 1: 2.5～3.5: 1.
6. as claimed in claim 1 three fluoridize the preparation method of ferrum nano material, it is characterized in that: heat treated temperature is 60-120 ℃ in the step (3), and heat treatment time is 2 hours-3 days.
7. three fluoridize ferrum nano material like what each described preparation method of claim 1-6 prepared.
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| CN103151523A (en) * | 2013-02-28 | 2013-06-12 | 湘潭大学 | Preparation method of cuboid-shaped positive-pole FeF3(H2O)0.33 material |
| CN103165888A (en) * | 2013-03-02 | 2013-06-19 | 合肥国轩高科动力能源股份公司 | Preparation method of ferric three fluoride (FeF3) nanorod with embedded lithium activity |
| CN103682340A (en) * | 2013-12-26 | 2014-03-26 | 中国科学院上海硅酸盐研究所 | Iron-based fluoride nano material with hierarchical structure, preparation method and application thereof |
| CN103708565A (en) * | 2014-01-06 | 2014-04-09 | 贵州万方铝化科技开发有限公司 | Preparation method of FeF3 |
| CN103771534A (en) * | 2014-02-26 | 2014-05-07 | 贵州万方铝化科技开发有限公司 | Method and equipment for recycling fluoride in iron-containing compound production |
| CN104600301A (en) * | 2015-01-22 | 2015-05-06 | 中国工程物理研究院化工材料研究所 | Spherical cobaltous fluoride for battery positive material and preparation method of spherical cobaltous fluoride |
| CN105336946A (en) * | 2015-09-28 | 2016-02-17 | 中国船舶重工集团公司第七一二研究所 | Preparation method of ferric fluoride cathode material for lithium ion battery |
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| CN110713242A (en) * | 2019-08-09 | 2020-01-21 | 中国科学院地理科学与资源研究所 | Zero-valent iron material Fe @ iron fluoride and preparation method thereof |
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| CN103151523B (en) * | 2013-02-28 | 2015-07-22 | 湘潭大学 | Preparation method of cuboid-shaped positive-pole FeF3(H2O)0.33 material |
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| CN103165888B (en) * | 2013-03-02 | 2016-12-28 | 合肥国轩高科动力能源有限公司 | One has embedding lithium active Fe F3the preparation method of nanometer rods |
| CN103165888A (en) * | 2013-03-02 | 2013-06-19 | 合肥国轩高科动力能源股份公司 | Preparation method of ferric three fluoride (FeF3) nanorod with embedded lithium activity |
| CN103682340A (en) * | 2013-12-26 | 2014-03-26 | 中国科学院上海硅酸盐研究所 | Iron-based fluoride nano material with hierarchical structure, preparation method and application thereof |
| CN103708565B (en) * | 2014-01-06 | 2015-06-03 | 贵州万方铝化科技开发有限公司 | Preparation method of FeF3 |
| CN103708565A (en) * | 2014-01-06 | 2014-04-09 | 贵州万方铝化科技开发有限公司 | Preparation method of FeF3 |
| CN103771534B (en) * | 2014-02-26 | 2015-06-03 | 贵州万方铝化科技开发有限公司 | Method and equipment for recycling fluoride in iron-containing compound production |
| CN103771534A (en) * | 2014-02-26 | 2014-05-07 | 贵州万方铝化科技开发有限公司 | Method and equipment for recycling fluoride in iron-containing compound production |
| CN104600301A (en) * | 2015-01-22 | 2015-05-06 | 中国工程物理研究院化工材料研究所 | Spherical cobaltous fluoride for battery positive material and preparation method of spherical cobaltous fluoride |
| CN104600301B (en) * | 2015-01-22 | 2017-02-01 | 中国工程物理研究院化工材料研究所 | Spherical cobaltous fluoride for battery positive material and preparation method of spherical cobaltous fluoride |
| CN105336946A (en) * | 2015-09-28 | 2016-02-17 | 中国船舶重工集团公司第七一二研究所 | Preparation method of ferric fluoride cathode material for lithium ion battery |
| CN105958020A (en) * | 2016-05-26 | 2016-09-21 | 湘潭大学 | Method for preparing nanometer FeF<3>.0.33H<2>O by alcohol-thermal method |
| CN106099074A (en) * | 2016-08-19 | 2016-11-09 | 广东工业大学 | A kind of modified fluorinated ferrum nano composite anode material and its preparation method and application |
| CN106099074B (en) * | 2016-08-19 | 2019-03-22 | 广东工业大学 | A kind of modified fluorinated iron nano composite anode material and its preparation method and application |
| CN110713242A (en) * | 2019-08-09 | 2020-01-21 | 中国科学院地理科学与资源研究所 | Zero-valent iron material Fe @ iron fluoride and preparation method thereof |
| CN110713242B (en) * | 2019-08-09 | 2020-12-01 | 中国科学院地理科学与资源研究所 | Zero-valent iron material Fe @ iron fluoride and preparation method thereof |
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