CN103078110B - Monoclinic FeSO4·H2O and triclinic LifeXM1-XSO4F (M=Co, ni,0≤X≤1) preparation methods - Google Patents
Monoclinic FeSO4·H2O and triclinic LifeXM1-XSO4F (M=Co, ni,0≤X≤1) preparation methods Download PDFInfo
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Abstract
The invention provides the preparation method of a kind of lithium ion anode material iron system fluorosulfuric acid lithium, its precursor power is by FeSO
47H
2under vacuum, thermal dehydration, then passes into nitrogen to O, then heats, and makes a kind of presoma FeSO of bulk, porous, mutually pure anode material for lithium-ion batteries
4h
2o, structure is monoclinic phase, C2/C space group.By the presoma FeSO of obtained bulk, porous
4h
2o and MSO
4h
2o (M=Co, Ni) mixes with LiF, after heating with solvent ball milling, obtain target product LiFe
xm
1-xsO
4f (M=Co, Ni, 0≤X≤1), structure is three monoclinic phases, P1 space group.
Description
[technical field]
The present invention relates to lithium ion anode material iron system fluorosulfuric acid lithium LiFe
xm
1-xsO
4the preparation method of F (M=Co, Ni, x=0-1.0) and presoma thereof.The method overcome additive method preparation temperature high, atmosphere requirements is tight, and is difficult to obtain the shortcomings such as phase pure material, and preparation method is gentle, environmental protection, is applicable to large-scale production.
[background technology]
The positive electrode of lithium ion battery experienced by and constantly improves and creation process: from LiCoO
2to LiCoxNiyMnzO
2(x+y+z=1) LiFePO is arrived again
4, these materials differ from one another, but are also subject to different restrictions respectively in resource, price, environmental protection, safety etc., the more advanced at present and LiFePO of use of large-scale production
4, because electronics, ionic mobility are low, poorly conductive, must make its nanometer or carbon coated actually use.In the process route that they are all, all include refractory ceramics measure, structure, character are difficult to effective control, and process conditions are harsh, and process is complicated, and cost is higher.LiFe
xm
1-xsO
4f (M=Co, Ni; X=0-1.0) having good ion, electron transport ability and good oxidation-reduction quality because of the structure of its advanced person, therefore have good chemical property, is a kind of new type lithium ion positive electrode.This material can not adopt solid phase reaction, because just decompose 400 DEG C time, again because its facile hydrolysis, can not adopt aqueous phase reactions, can only use FeSO
4.H
2o makes presoma and LiF adopts the hot method of ion and the preparation of solvent structure route.Via the FeSO of cheapness
4.7H
2o prepares its presoma, and usual methods availalbe is: 1,200 DEG C of heating in vacuum dehydration in 1 hour; 2, under the atmosphere of nitrogen and hydrogen, 100 DEG C of heating dehydration in 3 hours.These two kinds of methods the former owing to being heating in vacuum 200 DEG C, temperature is higher, can make FeSO
4h
2o lumps, and the presoma obtained is bulk not, porous, affects reaction medium and its effect and unfavorable ion-exchange reactions is carried out.The latter is low due to temperature, dehydration can be made not thorough, can not obtain pure phase product, and atmosphere is complicated, controls trouble.The method that one of the present invention adopts vacuum and nitrogen stream to drive protection prepares presoma.Flowing nitrogen atmosphere also has except ensureing the environment of sample preparation accelerates moisture evaporation rate; effectively improve dewatering speed and the degree of dehydration of course of reaction; intake valve in addition on device and air outlet valve can switch rapidly and regulate under vacuum or nitrogen protection state; thus effectively can control dewatering speed and the degree of dehydration of course of reaction, the FeSO that the method is obtained
4.H
2o is bulk, porous and mutually pure monoclinic crystal, C2/C space group.
Current preparation LiFeSO
4f has two kinds of methods: one, the hot method of ion; Two, solvent-thermal method, these two kinds of methods are all utilize solvent to go to dissolve LiF, make generation ion-exchange.Product LiFe
xm
1-xsO
4f (M=Co, Ni; X=0-1.0) three monoclinic phases are belonged to, P1 space group, it and LiFeSO
4f belongs to a series of in composition, configuration aspects.According to by presoma to the topology rule of product and the phase principle of similitude, require FeSO
4.H
2o is monoclinic phase that is bulk and C2/C space group, resets the new material of composition metastable phase under ion heat, solvent heat technique.This material is metastable phase polyanionic compound, is because they can be regarded as by Li
+, Fe
2+, M
2+, O
2-the LiO formed
6, FeO
6, MO
6(M=Co, Ni) octahedra anion and SO
4 2-tetrahedral anion, at F
-under existence, these anion adopt nonadjacent oxygen atom altogether to connect into the structure with three-dimensional tunnel according to certain orientation, and this tunnel structure architecture is in Li
+migration, thus this material has special significance in lithium ion cell electrode positive electrode investigation and application.The hot method of ion selects EMI-TESI (1-ethyl-3-methylimidazole quinoline-bis trifluoromethyl sulphonyl imine) to be ionic liquid, can obtain good LiFeSO
4f and LiFe
xm
1-xsO
4f, but ionic liquid is expensive, course of reaction synthesis temperature is higher, 300 DEG C, and is also difficult to mutually pure, and if solvent-thermal method is selected reaction medium and is applicable to synthetic reaction, its low price many, preparation temperature is also low, controls well, and obtained sample is mutually pure.The reported first such as RajeshTripathi was made reaction medium with simple tetraethylene glycol and was adopted solvent-thermal method to successfully synthesize the LiFeSO of polyanionic compound Tavorite type in October, 2010
4f and NaFeSO
4f.Obtained product conductive capability and Heat stability is good, cyclic reversibility is splendid, but operating procedure is more loaded down with trivial details, is unfavorable for large-scale production.
[summary of the invention]
The solvent-thermal method of the present invention passes through monoclinic phase presoma Fe that is bulk, porous
xm
1-XsO
4h
2o and LiF mixes, and adds the polyalcohol formation dicyandiamide solution that tetraethylene glycol is equipped with higher, carries out ball milling and heating, obtained LiFe
xm
1-xsO
4f.Reaction principle is expressed as: HFe
xm
1XsO
4oH+LiF → LiFe
xm
1-xsO
4f+H
2o (M=Co, Ni; X=0-1.0), be an ion exchange process.Dicyandiamide solution, by the combination of different solvents, controls reaction process, reaches quickening ion-exchange reactions, improves domain size distribution, optimizes LiFe
xm
1-xsO
4f pattern, make it more even, size is more reasonable, and course of reaction is more simple, is applicable to large-scale production, and the LiFe of preparation
xm
1-xsO
4f phase is very pure.
The invention process process:
By FeSO
47H
2o (CoSO
47H
2o/NiSO46H
2o) add reactor, maintain vacuum degree-0.1MPa and be heated to 150 DEG C of maintenances 1 hour.Under the atmosphere of 0.1Mpa ~ 0.3Mpa flow of nitrogen gas, continue at 150 DEG C of (NiSO
46H
2o is 200 DEG C) heat 2 hours.
By monoclinic phase presoma FeSO that is bulk, porous
4h
2o (or the Fe be made into
1-xm
xsO
4) and LiF with 1: 1.1-1: 1.2 thing mass ratio mixing after put into reactor, add and FeSO
4h
2o and LiF total weight ratio is the zirconium ball of 15: 1, and add 30ml tetraethylene glycol solvent system (the 5%-10% glycerol of volume), tighten the lid of reactor, carry out ball milling, the time is 12-16 hour simultaneously.
Reactor after ball milling is put into baking oven to carry out adding thermal response, temperature is 220 DEG C, heats 60 hours, the concussion of limit border ring interval ball milling.Reacted sample acetone washs, then suction filtration, dries, then carries out composition and structure detection.
Advantage of the present invention is: obtained product conductive capability and Heat stability is good, and cyclic reversibility is splendid; Operating procedure is simple and convenient, mild condition, and equipment is simple; Presoma and target product structure, character are easy to control, are applicable to large-scale production; Reaction environment is friendly, energy savings.
[accompanying drawing explanation]
Fig. 1 is FeSO
4h
2the XRD figure of O.
Fig. 2 is LiFe
1-xco
xsO
4the XRD figure of F, wherein X=0,0.2,0.6,1.0, be designated as a, b.c, d.
Fig. 3 is LiFe
1-xni
xsO
4the XRD figure of F, wherein X=0,0.4,0.6,1.0, be designated as a, b.c, d.
[
embodiment]
One, precursor power
1. claim 155.10gFeSO
47H
2o is placed in oil bath reactor, reactor must seal, vacuumize, vacuum degree maintenance-0.1MPa, opens heating simultaneously, treat that temperature rises to 150 DEG C and maintains 1 hour, close vacuum and open nitrogen valve, open atmospheric valve, reaction unit internal pressure remains 0.1MPa, 150 DEG C of heating 2 hours, obtain bulk and constituent analysis meets FeSO
4h
2o product forms.XRD test analysis is mutually pure monoclinic phase, C2/C space group.XRD is shown in Fig. 1.
2. claim 155.10gFeSO
47H
2o is placed in as in finish application bath reactor, reactor must seal, vacuumize, vacuum degree maintenance-0.1MPa, opens heating simultaneously, treat that temperature rises to 150 DEG C and maintains 1 hour, close vacuum and open nitrogen valve, open atmospheric valve, reaction unit internal pressure remains 0.2MPa, 150 DEG C of heating 2 hours, obtain bulk and constituent analysis meets FeSO
4h
2o forms.XRD test analysis is mutually pure monoclinic phase, C2/C space group.The same Fig. 1 of XRD.
3. claim 155.10gFeSO
47H
2o is placed in as in finish application bath reactor, reactor must seal, vacuumize, vacuum degree maintenance-0.1MPa, opens heating simultaneously, treat that temperature rises to 150 DEG C and maintains 1 hour, close vacuum to open into nitrogen valve, open atmospheric valve, reaction unit internal pressure remains 0.3MPa, 150 DEG C of heating 2 hours, obtain bulk and constituent analysis meets FeSO
4h
2o forms.XRD test analysis is mutually pure monoclinic phase, C2/C space group.The same Fig. 1 of XRD.
4. claim 100.00gCoSO
47H
2o is placed in as in finish application bath reactor, reactor must seal, vacuumize, vacuum degree maintenance-0.1MPa, opens heating simultaneously, treat that temperature rises to 150 DEG C and maintains 1 hour, close vacuum and pass into nitrogen, open atmospheric valve, reaction unit internal pressure remains 0.2MPa, 150 DEG C of heating 2 hours, obtain bulk and constituent analysis meets CoSO
4h
2o product forms.XRD test analysis is mutually pure monoclinic phase, C2/C space group.The similar Fig. 1 of XRD.
5. claim 100.00gNiSO
46H
2o is placed in as in finish application bath reactor, reactor must seal, vacuumize, vacuum degree maintenance-0.1MPa, opens heating simultaneously, treat that temperature rises to 150 DEG C and maintains 1 hour, close vacuum and pass into nitrogen, open atmospheric valve, reaction unit internal pressure remains 0.2MPa, 200 DEG C of heating 2 hours, obtain bulk while constituent analysis meets NiSO
4h
2o product forms.XRD test analysis is mutually pure monoclinic phase, C2/C space group.The similar Fig. 1 of XRD.
6. claim 111.20gFeSO
47H
2o and 28.11gCoSO
47H
2o is placed in as in finish application bath reactor, reactor must seal, vacuumize, vacuum degree maintenance-0.1MPa, treats that temperature rises to 150 DEG C and maintains 1 hour, closes vacuum and pass into nitrogen, open atmospheric valve, reaction unit internal pressure remains 0.2MPa, and 150 DEG C of heating 2 hours, obtain bulk and constituent analysis meets Fe
0.6co
0.4sO
4h
2o product forms.XRD test analysis is mutually pure monoclinic phase, C2/C space group.The similar Fig. 1 of XRD.
7. claim 83.40gFeSO
47H
2o and 56.20gCoSO
47H
2o is placed in as in finish application bath reactor, and reactor must seal, and vacuumizes, vacuum degree maintenance-0.1MPa, treat that temperature rises to 150 DEG C, close vacuum and pass into nitrogen, open atmospheric valve, reaction unit internal pressure remains 0.2MPa, and 150 DEG C of heating 2 hours, obtain bulk and constituent analysis meets Fe
0.6co
0.4sO
4h
2o product forms.XRD test analysis is mutually pure monoclinic phase, C2/C space group.The similar Fig. 1 of XRD.
8. claim 69.50gFeSO
47H
2o and 70.25gCoSO
47H
2o is placed in as in finish application bath reactor, and reactor must seal, and treats that temperature rises to 150 DEG C, and close vacuum and pass into nitrogen, open atmospheric valve, reaction unit internal pressure remains 0.2MPa, and 150 DEG C of heating 2 hours, obtain bulk and constituent analysis meets Fe
0.5co
0.5sO
4h
2o product forms, and XRD test analysis is mutually pure monoclinic phase, C2/C space group.The similar Fig. 1 of XRD.
Two, LiFe
xm
1-xsO
4prepared by F
1. claim the monoclinic phase presoma FeSO of bulk, the porous of 10.0081g
4h
2o and 1.6803gLiF is placed in (see our company's practicality invention " a kind of ion heat, solvent thermal reaction device preparing iron system fluorosulfuric acid salt ") in reactor, take 175.00g zirconium ball again to add reactor and expect to mix, then tetraethylene glycol and the 1.5ml glycerol of 30ml is added, tighten chamber lid, reactor is put in sample pulverizer and carries out vibration 12 hours, vibrate complete, put into baking oven, temperature rises to 220 DEG C, add thermal response 60 hours, finally take out the washing of product acetone, suction filtration, obtains product.Constituent analysis meets LiFeSO
4the composition of F, XRD test analysis is three mutually pure monoclinic phases, P1 space group.XRD is shown in Fig. 2-a.
2. claim monoclinic phase presoma 10.0056gFeSO that is bulk, porous
4h
2o and 1.6798gLiF is placed in as above in reactor, take 175.00g zirconium ball again to add reactor and expect to mix, then add tetraethylene glycol and the 3ml glycerol of 30ml, tighten chamber lid, reactor is put in sample pulverizer and carries out vibration 16 hours, vibrate complete, put into baking oven, temperature rises to 220 DEG C, add thermal response 60 hours, finally take out the washing of product acetone, suction filtration, obtains product.Constituent analysis meets LiFeSO
4the composition of F.XRD test analysis is three mutually pure monoclinic phases, P1 space group.The same Fig. 2 of XRD-a.
3. claim monoclinic phase presoma 10.0021gCoSO that is bulk, porous
4h
2o and 1.5116gLiF is placed in as above in reactor, take 173.00g zirconium ball again to add reactor and expect to mix, then add tetraethylene glycol and the 1.5ml glycerol of 30ml, tighten chamber lid, reactor is put in sample pulverizer and carries out vibration 12 hours, vibrate complete, put into baking oven, temperature rises to 220 DEG C, add thermal response 60 hours, finally take out the washing of product acetone, suction filtration, obtains product.Constituent analysis meets LiCoSO
4the composition of F.XRD test analysis is three mutually pure monoclinic phases, P1 space group.XRD is shown in Fig. 2-d.
4. claim monoclinic phase presoma 9.9953gNiSO that is bulk, porous
4h
2o and 1.6485gLiF is placed in as above in reactor, take 175.00g zirconium ball again to add reactor and expect to mix, then add tetraethylene glycol and the 1.5ml glycerol of 30ml, tighten chamber lid, reactor is put in sample pulverizer and carries out vibration 12 hours, vibrate complete, put into baking oven, temperature rises to 220 DEG C, adds thermal response 60 hours, finally take out the washing of product acetone, suction filtration.Constituent analysis meets LiNiSO
4f product forms, and XRD test analysis is three mutually pure monoclinic phases, P1 space group.XRD is shown in Fig. 3-d.
5. claim monoclinic phase presoma 10.1001gFe that is bulk, porous
0.8co
0.2sO
4h
2o and 1.7003gLiF is placed in as above in reactor, take 177.00g zirconium ball again to add reactor and expect to mix, then add tetraethylene glycol and the 1.5ml glycerol of 30ml, tighten chamber lid, reactor is put in sample pulverizer and carries out vibration 12 hours, vibrate complete, put into baking oven, temperature rises to 220 DEG C, adds thermal response 60 hours, finally take out the washing of product acetone, suction filtration.Constituent analysis meets LiFe
0.8co
0.2sO
4f product forms, and XRD test analysis is three mutually pure monoclinic phases, P1 space group.XRD is shown in Fig. 2-b
6. claim monoclinic phase presoma 10.1011gFe that is bulk, porous
0.4co
0.6sO
4h
2o and 1.7015gLiF is placed in as above in reactor, take 177.00g zirconium ball again to add reactor and expect to mix, then add tetraethylene glycol and the 1.5ml glycerol of 30ml, tighten chamber lid, reactor is put in sample pulverizer and carries out vibration 12 hours, vibrate complete, put into baking oven, temperature rises to 220 DEG C, add thermal response 60 hours, finally take out the washing of product acetone, suction filtration, obtains product.Constituent analysis meets LiFe
0.4co
0.6sO
4f forms, and XRD test analysis is three mutually pure monoclinic phases, P1 space group.XRD is shown in Fig. 2-c.
7. claim monoclinic phase presoma 7.9991gFeSO that is bulk, porous
4h
2o, 2.0362gCoSO
4h
2o and 1.6907gLiF is placed in as above in reactor, take 175.00g zirconium ball again to add reactor and expect to mix, then add tetraethylene glycol and the 1.5ml glycerol of 30ml, tighten chamber lid, reactor is put in sample pulverizer and carries out vibration 12 hours, vibrate complete, put into baking oven, temperature rises to 220 DEG C, add thermal response 60 hours, finally take out the washing of product acetone, suction filtration, obtains product.Constituent analysis meets LiFe
0.8co
0.2sO
4f forms.XRD test analysis is three mutually pure monoclinic phases, P1 space group.The same Fig. 2 of XRD-b.
8. claim monoclinic phase presoma 4.0011gFeSO that is bulk, porous
4h
2o, 6.1088gCoSO
4h
2o and 1.6907gLiF is placed in as above in reactor, take 175.00g zirconium ball again to add reactor and expect to mix, then add tetraethylene glycol and the 1.5ml glycerol of 30ml, tighten chamber lid, reactor is put in sample pulverizer and carries out vibration 12 hours, vibrate complete, put into baking oven, temperature rises to 220 DEG C, add thermal response 60 hours, finally take out the washing of product acetone, suction filtration, obtains product.Constituent analysis meets LiFe
0.4co
0.6sO
4f forms.XRD test analysis is three mutually pure monoclinic phases, P1 space group.The same Fig. 2 of XRD-c.
9. claim monoclinic phase presoma 6.0101gFeSO that is bulk, porous
4h
2o, 4.0671gNiSO
4h
2o and 1.6809gLiF is placed in reactor, take 175.00g zirconium ball again to add reactor and expect to mix, then add tetraethylene glycol and the 1.5ml glycerol of 30ml, tighten chamber lid, reactor is put in sample pulverizer and carries out vibration 12 hours, vibrate complete, put into baking oven, temperature rises to 220 DEG C, add thermal response 60 hours, finally take out the washing of product acetone, suction filtration, obtains product.Constituent analysis meets LiFe
0.6ni
0.4sO
4f forms.XRD test analysis is three mutually pure monoclinic phases, P1 space group.See Fig. 3-b.
10. claim monoclinic phase presoma 4.0076gFeSO that is bulk, porous
4h
2o, 6.1001gNiSO
4h
2o and 1.6809gLiF is placed in reactor, take 175.00g zirconium ball again to add reactor and expect to mix, then add tetraethylene glycol and the 1.5ml glycerol of 30ml, tighten chamber lid, reactor is put in sample pulverizer and carries out vibration 12 hours, vibrate complete, put into baking oven, temperature rises to 220 DEG C, add thermal response 60 hours, finally take out the washing of product acetone, suction filtration, obtains product.Constituent analysis meets LiFe
0.4ni
0.6sO
4f forms.XRD test analysis is three mutually pure monoclinic phases, P1 space group.See Fig. 3-c.
Claims (3)
1. an anode material for lithium-ion batteries iron system fluorosulfuric acid lithium compound LiFe
xm
1-xsO
4the preparation method of F, wherein, M=Co, Ni, 0≤X≤1, the preparation method of this compound adopts the mixed system of glycerol and tetraethylene glycol to make solvent, by monoclinic phase presoma FeSO that is bulk, porous
4h
2o and NiSO
4h
2o or CoSO
4h
2o mixes in proportion, and LiF is placed in reactor and carries out solvent thermal reaction, and this reactor is that ball milling device and reactor are same, ball-milling medium and reaction medium same.
2. a kind of anode material for lithium-ion batteries iron system fluorosulfuric acid lithium compound LiFe as claimed in claim 1
xm
1-xsO
4the preparation method of F, the mixed system solvent that it is characterized in that wherein be glycerol with tetraethylene glycol by volume 5%-10% mix.
3. a kind of anode material for lithium-ion batteries iron system fluorosulfuric acid lithium compound LiFe as claimed in claim 1
xm
1-xsO
4the preparation method of F, wherein bulk, porous monoclinic phase presoma FeSO
4h
2o, NiSO
4h
2o and CoSO
4h
2the preparation of O is by FeSO
47H
2o and CoSO
47H
2o is placed in dehydration reactor 150 DEG C of heating in vacuum 1 hour, then under the flowing nitrogen of 0.01-0.03MPa, and 150 DEG C of constant temperature 2 hours; By NiSO
46H
2o is placed in reaction unit 150 DEG C of heating in vacuum 1 hour, then under the flowing nitrogen of 0.01-0.03MPa, and 200 DEG C of constant temperature 2 hours.
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| CN107230779B (en) * | 2017-05-03 | 2021-02-19 | 武汉理工大学 | Preparation method of high-temperature stable phase-change type lithium iron fluorosulfate battery material, electrode plate and use method of lithium ion battery |
| CN106920965A (en) * | 2017-05-10 | 2017-07-04 | 江西理工大学 | A kind of new sodium ion positive electrode NaFeSO4The preparation method of F |
| CN113793933B (en) * | 2021-09-10 | 2023-05-30 | 深圳市研一新材料有限责任公司 | Lithium sulfide for solid electrolyte and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1659728A (en) * | 2001-10-26 | 2005-08-24 | 化合价技术股份有限公司 | Alkali/transition metal halo-and hydroxy-phosphates and related electrode active materials |
-
2011
- 2011-10-26 CN CN201110328858.7A patent/CN103078110B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1659728A (en) * | 2001-10-26 | 2005-08-24 | 化合价技术股份有限公司 | Alkali/transition metal halo-and hydroxy-phosphates and related electrode active materials |
Non-Patent Citations (2)
| Title |
|---|
| Scalable Synthesis of Tavorite LiFeSO4F and NaFeSO4F Cathode Materials;Rajesh Tripathi等;《Angew. Chem.》;20101108;第8920-8924页 * |
| Structure and electrochemical properties of novel mixed Li(Fe1-xMx)SO4F(M=Co, Ni, Mn) phases fabricated by low temperature ionothermal synthesis;Prabeer Barpanda等;《Journal of Materials Chemistry》;20100119;第1659-1668页 * |
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