CN103078111B - Preparation method of monoclinic FeSO4·H2O and triclinic NaFe1-xMxSO4F (M=Co, ni) - Google Patents

Preparation method of monoclinic FeSO4·H2O and triclinic NaFe1-xMxSO4F (M=Co, ni) Download PDF

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CN103078111B
CN103078111B CN201110328862.3A CN201110328862A CN103078111B CN 103078111 B CN103078111 B CN 103078111B CN 201110328862 A CN201110328862 A CN 201110328862A CN 103078111 B CN103078111 B CN 103078111B
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nafe
acetone
glycerol
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CN103078111A (en
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沈晓彦
王骁瑜
俞春健
陈东
胡炳华
陆凯钻
崔冬梅
陈睿
缪卫东
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YANTAI SHUCHI VEHICLE CO Ltd
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Nantong Lichi Energy Technology Co ltd
Jiangsu Highstar Battery Manufacturing Co ltd
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Abstract

This patent provides preparation three monoclinic phase NaFe 1-xm xsO 4f (M=Co, Ni; 0 < X≤1) method, comprising monoclinic phase presoma FeSO that is bulk, porous 4h 2namely the preparation of O is by FeSO 47H 2o fully mixes with sodium hydrosulfite, thermal dehydration, then obtains through absolute methanol backflow.By obtained FeSO 4h 2o and MSO4H 2o (M=Co, Ni) mixing obtains target product NaFe with the NaF of chemical dose by solvent thermal reaction again 1-xm xsO 4(M is Co, Ni to F; 0 < X≤1), structure is three monoclinic phases, P1 space group.

Description

Monoclinic phase FeSO 4h 2o and three monoclinic phase NaFe 1-xm xsO 4f (M=Co, Ni) preparation method
[technical field]
The present invention relates to the preparation method of a kind of novel polyanionic compound sodium ion conductor, sodion solid electrolytes and sodium-ion battery electrode anode material.
Three monoclinic phase NaFe 1-xm xsO 4f is Tavorite type (water phosphorus lithium iron-stone) structure, monoclinic phase FeSO 4h 2o and NaFe 1-xm xsO 4topological relation is had by the phase principle of similitude between F.So monoclinic phase FeSO 4h 2o is as preparation three monoclinic phase NaFe 1-xm xsO 4the presoma of this metastable phase new material of F.So-called NaFe 1-xm xsO 4f is metastable phase polyanionic compound, is because they can be regarded as by Na +, Fe 2+, M 2+(M=Co, Ni), O 2-the NaO formed 6, FeO 6, MO 6(M=Co, Ni) octahedra anion and SO 4tetrahedral anion, at F -under existence, adopt nonadjacent oxygen atom altogether to connect into the structure with three-dimensional tunnel according to certain orientation, this tunnel structure is suitable for Na +, Li +deng alkali ion movement, thus this material has special significance in sodium ion conductor, sodion solid electrolytes and the investigation of materials of sodium-ion battery electrode anode and application aspect, especially as sodium-ion battery electrode anode material.The present invention includes two parts, a part is FeSO 47H 2o dehydration generates monoclinic phase presoma FeSO that is bulk, porous 4h 2o, a part is obtained FeSO 4h 2o and MSO4H 2o (M=Co, Ni) mixing obtains target product NaFe with the NaF of chemical dose by solvent thermal reaction again 1-xm xsO 4f (M=Co, Ni; 0 < X≤1).
Prepare target product NaFe 1-xm xsO 4f (M=Co, Ni; 0 < X≤1) presoma is required: one is pure monoclinic phase FeSO 4h 2o, two is that particle diameter is little and bulk, porous.FeSO 47H 2o dehydration generates monoclinic phase presoma method that is bulk, porous to be had: 1. heat 1 hour in 200 DEG C of vacuum; 2. under the atmosphere of nitrogen and hydrogen, 100 DEG C of heating 3 hours.The shortcoming of these two kinds of methods: the former because temperature is higher, can make FeSO owing to being heating in vacuum 200 DEG C 4h 2o lumps, and the presoma obtained is fluffy not, and the latter is low due to temperature, dehydration can be made not thorough, and atmosphere is complicated, controls trouble.The present invention makes FeSO to reach 4h 2o is bulk, porous, prevents oxidation, adopts sodium hydrosulfite auxiliary heating dewatering, because oxygen consumed solid/liquid/gas reactions easily occurs sodium hydrosulfite:
2S 2o 4 2-+ O 2+ 4OH -→ 4SO 3 2-+ 2H 2o is so effectively can prevent FeSO 4be oxidized, unnecessary sodium hydrosulfite is soluble in absolute methanol, and backflow can remove sodium hydrosulfite, just obtains the monoclinic phase presoma of satisfactory bulk, porous after driving absolute methanol away.Its method is simple, effective.Target product synthesis solvent-thermal method, according to reacting as follows:
FeSO 4·H 2O+NaF→NaFeSO 4F+H 2O
FeSO 4·H 2O+NaF→NaFeSO 4F+H 2O
Or FeSO 4h 2o+M xsO 4h 2o+NaF → NaFe 1-xm xsO 4f+H 2o (M=Co, Ni; 0 < X≤1)
Preparation method: experimentation of the present invention fully grinds for taking NaF, until powder becomes flowing water shape fine and smooth, then adds the monoclinic phase presoma FeSO of bulk, porous of corresponding mol ratio 4h 2o (or FeSO 4h 2o and MSO 4h 2the compound of O), with acetone as the abundant ground and mixed of medium, acetone of rushing is moved in reactor, the tetraethylene glycol added and mixed system (a small amount of glycerol and ethylene glycol) thereof fully stir and seal, put into heating cabinet, temperature is set as 220 DEG C, dries 48h.Washed by the product acetone obtained, suction filtration is dried, and namely obtains NaFeSO 4f (or NaFe 1-xm xsO 4f).In tetraethylene glycol, add the effect that a small amount of polyalcohol can play water suction, promote the process of reaction, can also pattern be improved, make size evenly more reasonable.
Sodium-ion battery is another best, up-to-date selection for rechargeable battery, although Li-Ion rechargeable battery has good charge storage ability, but due to expensive and restriction is a large amount of produces and application, thus be expected to allow sodium ion rechargeable battery become alternative lithium ion battery, for large scale storage electric energy, cheap new way.The preparation method of the sodium-ion battery before invented is the hot method of ion, but system is complicated, and expensive, synthesis temperature is higher, 300 DEG C, is also difficult to pure mutually.Wherein NaFePO 4own poorly conductive (electronic and ionic mobility is low), its nanometer or carbon coated must be made actually to use, meaning will pass through high temperature process heat, this is just difficult to the character and the structure that reach manual control, so add complexity and the cost of technique, the more important thing is that it also fails to meet fail safe and practicality problem comprehensively.The new sodium ion positive electrode NaFeSO of in October, 2010 reported first such as Rejesh Tripathi 4f.It adopts solvent-thermal method preparation, the sodium ion positive electrode NaFeSO that the method is obtained 4f, for NaFePO before 4positive electrode is a very large leap.NaFePO 4or NaFe 1-xm xsO 4f is a kind of metastable phase, its good conductivity, does not need carbon coated just can use, and just can synthesize, so its structure, character can control very well at low temperatures.
The invention process process is divided into:
1. by FeSO 47H 2o and sodium hydrosulfite in mass ratio 3: 1---5: 1 Homogeneous phase mixing are placed in crucible to be put into 150 DEG C of baking oven vacuum dehydrations and dries 3 hours to obtain FeSO 4h 2the mixture of O and sodium hydrosulfite.
2. carrying out backflow with absolute methanol to mixture obtains mutually pure, the monoclinic phase intermediate FeSO of bulk, porous 4h 2o.
3. be 1: 1.1 by Fe and Na atomic ratio---take NaF at 1: 1.2 fully grinds, until powder becomes flowing water shape fine and smooth, then is 1: 1.1 by Fe and Na atomic ratio---add FeSO at 1: 1.2 4h 2o, with acetone as the abundant ground and mixed of medium, acetone of rushing is moved in reactor, the tetraethylene glycol mixed system (glycerol of the 3%-15% of volume and ethylene glycol) adding 30ml fully stirs and seals, put into heating cabinet, temperature is set as 220 DEG C, dries 48h.Washed by the product acetone obtained, suction filtration is dried.
4., in special reactor, be take FeSO at 1: 1.1 by Fe and Na atomic ratio 4h 2o and NaF, add appropriate tetraethylene glycol mixed system (glycerol of the 3%-15% of volume and ethylene glycol) and zirconium ball, tighten reactor and be placed in sample pulverizer, put into 220 DEG C of baking ovens baking 48h. after ball milling 12h-16h and washed by the product acetone obtained, suction filtration is dried.
5. take appropriate COSO 47H 2the baking oven vacuum dehydration that O is placed in 150 DEG C in crucible is dried and within 3 hours, is obtained monoclinic phase presoma COSO that is bulk, porous 4h 2o.
6. take appropriate NiSO 46H 2the baking oven vacuum dehydration that O is placed in 200 DEG C in crucible is dried and within 3 hours, is obtained monoclinic phase presoma NiSO that is bulk, porous 4h 2o.
7. use COSO 4h 2o, NiSO 4h 2o or a certain amount of COSO 4h 2o and NiSO 4h 2o and FeSO 4h 2o mixture substitutes FeSO in the 3rd step 4h 2o, the product obtained is NaFe 1-xm xsO 4f (M=Co, Ni; 0 < X≤1).
Advantage of the present invention is:
1. novel sodium ion positive electrode NaFeSO 4f or NaFe 1-xm xsO 4f (M=Co, Ni; 0 < X≤1) good conductivity, not needing carbon coated just can use, and just can synthesize at low temperatures, is metastable phase, so its structural property controls very well.
2. the FeSO of preparation 4h 2o is bulk, porous, Xiang Chun, and sodium hydrosulfite low price is easy to use.
3. equipment is simple, and suitable for mass production is applied.
[accompanying drawing explanation]
Fig. 1 is FeSO 4h 2the XRD figure of O.
Fig. 2 is COSO 4h 2the XRD figure of O.
Fig. 3 is NiSO 4h 2the XRD figure of O.
Fig. 4 is NaFeSO 4the SEM figure of F.
Fig. 5 is NaFeSO 4the XRD figure of F.
[embodiment]
One, the preparation of presoma:
1. claim 20gFeSO 47H 2o and 5g sodium hydrosulfite mixes puts into crucible, is placed in 150 DEG C of baking oven vacuum dehydrations and dries 3 hours to obtain FeSO 4h 2the mixture of O and sodium hydrosulfite, color is the mixture of grey black.Take 6g mixture to pour in 250ml flask, add 200ml absolute methanol and be placed on heating collar and carry out back flow reaction (jacket temperature is set as 68 DEG C).Often spend 20 minutes and change once new absolute methanol, each 200ml, change clothes 4 times.Finally add acetone suction filtration, dry in 100 DEG C of baking ovens.XRD figure visible structure is pure monoclinic phase, C2/C space group, sees Fig. 1.
2. claim 20gFeSO 47H 2o and 5g sodium hydrosulfite mixes puts into crucible, is placed in 150 DEG C of baking oven vacuum dehydrations and dries 3 hours to obtain FeSO 4h 2the mixture of O and sodium hydrosulfite, color is the mixture of grey black.Take 6g mixture to pour in 250ml flask, add 200ml absolute methanol and be placed in water-bath and carry out back flow reaction (water-bath temperature is set as 70 DEG C).Often spend 20 minutes and change once new absolute methanol, each 200ml, change clothes 4 times.Finally add acetone suction filtration, dry in 100 DEG C of baking ovens.XRD figure visible structure is pure monoclinic phase, C2/C space group, and class is as Fig. 1.
3. claim 30gFeSO 47H 2o and 10g sodium hydrosulfite mixes puts into crucible, is placed in 150 DEG C of baking oven vacuum dehydrations and dries 3 hours to obtain FeSO 4h 2the mixture of O and sodium hydrosulfite.Color is the mixture of grey black.Take 6g intermediate to pour in 250ml flask, add 200ml absolute methanol and be placed in water-bath and carry out back flow reaction (water-bath temperature is set as 70 DEG C).Often spend 20 minutes and change once new absolute methanol, each 200ml, change clothes 4 times, until sodium hydrosulfite is cleaned.Finally add acetone suction filtration, dry in 100 DEG C of baking ovens.XRD figure visible structure is pure monoclinic phase, C2/C space group, and class is as Fig. 1.
4. claim 25gFeSO 47H 2o and 5g sodium hydrosulfite mixes puts into crucible, is placed in 150 DEG C of baking oven vacuum dehydrations and dries 3 hours to obtain FeSO 4h 2the intermediate of O and sodium hydrosulfite.Its uneven color, some grey black, some limes, have caking phenomenon.Take 6g intermediate to pour in 250ml flask, add 200ml absolute methanol and be placed in water-bath and carry out back flow reaction (water-bath temperature is set as 70 DEG C).Often spend 20 minutes and change once new absolute methanol, each 200ml, changes clothes 3-4 time, until sodium hydrosulfite is cleaned.Finally add acetone suction filtration, dry in 100 DEG C of baking ovens.XRD figure visible structure is pure monoclinic phase, C2/C space group, and class is as Fig. 1.
5. claim 25g COSO 47H 2the baking oven vacuum dehydration that O is placed in 150 DEG C in crucible is dried and within 3 hours, is obtained monoclinic phase presoma COSO that is bulk, porous 4h 2o.XRD figure visible structure is pure monoclinic phase, C2/C space group, sees Fig. 2.
6. claim 28gNiSO 46H 2the baking oven vacuum dehydration that O is placed in 200 DEG C in crucible is dried and within 3 hours, is obtained monoclinic phase presoma NiSO that is bulk, porous 4h 2o.XRD figure visible structure is pure monoclinic phase, C2/C space group, sees Fig. 3.
Two, three monoclinic phase NaFe 1-xm xsO 4f (M=Co, Ni; 0 < X≤1) preparation method
1. claim 2.7090gNaF fully to grind until powder becomes flowing water shape fine and smooth in agate mortar, then add 9.9921gFeSO 4h 2o, with acetone as the abundant ground and mixed of medium, acetone of rushing is moved in reactor, the tetraethylene glycol mixed system (0.5ml glycerol and 0.5ml ethylene glycol) adding 30ml fully stirs and seals, put into heating cabinet, temperature is set as 220 DEG C, dries 48h.Washed by the product acetone obtained, suction filtration is dried.Its composition of analysis of components meets NaFeSO 4the SEM figure of F, XRD test analysis is three mutually pure monoclinic phases, and P1 space group, is shown in Fig. 4, Fig. 5.
2. claim 2.7361gNaF fully to grind until powder becomes flowing water shape fine and smooth in agate mortar, then add 10.069gFeSO 4h 2o, with acetone as the abundant ground and mixed of medium, acetone of rushing is moved in reactor, and the tetraethylene glycol mixed system (1ml glycerol and 1ml ethylene glycol) adding 30ml fully stirs and seals, and put into heating cabinet, temperature is set as 220 DEG C, dries 48h.Washed by the product acetone obtained, suction filtration is dried.Its composition of analysis of components meets NaFeSO 4f, XRD test analysis is three mutually pure monoclinic phases, and P1 space group, as Fig. 4, Fig. 5.
3. claim 2.7233gNaF fully to grind until powder becomes flowing water shape fine and smooth in agate mortar, then add 10.022gFeSO 4h 2o, with acetone as the abundant ground and mixed of medium, acetone of rushing is moved in reactor, and the tetraethylene glycol mixed system (2ml glycerol and 2ml ethylene glycol) adding 30ml fully stirs and seals, and put into heating cabinet, temperature is set as 220 DEG C, dries 48h.Washed by the product acetone obtained, suction filtration is dried.Its composition of analysis of components meets NaFeSO 4f, XRD test analysis is three mutually pure monoclinic phases, and P1 space group, as Fig. 4, Fig. 5.
4. take 9.9958g presoma FeSO 4h 2o and 2.7215gNaF, in special reactor, adds 30ml tetraethylene glycol and 170g zirconium ball, tightens reactor and be placed on sample pulverizer, and put into 220 DEG C of baking ovens baking 48h. after ball milling 12h and washed by the product acetone obtained, suction filtration is dried.Its composition of analysis of components meets NaFeSO 4f, XRD test analysis is three mutually pure monoclinic phases, and P1 space group, as Fig. 4, Fig. 5.
5. claim 2.4318gNaF fully to grind until powder becomes flowing water shape fine and smooth in agate mortar, then add 10.0070gCOSO 4h 2o, with acetone as the abundant ground and mixed of medium, acetone of rushing is moved in reactor, and the tetraethylene glycol mixed system (1ml glycerol and 1ml ethylene glycol) adding 30ml fully stirs and seals, and put into heating cabinet, temperature is set as 220 DEG C, dries 48h.Washed by the product acetone obtained, suction filtration is dried. and its composition of analysis of components meets NaCoSO 4f, XRD test analysis is three mutually pure monoclinic phases, and P1 space group, class is as Fig. 4, Fig. 5.
6. claim 2.6822gNaF fully to grind until powder becomes flowing water shape fine and smooth in agate mortar, then add 10.0007gNiSO 4h 2o, with acetone as the abundant ground and mixed of medium, acetone of rushing is moved in reactor, and the tetraethylene glycol mixed system (1ml glycerol and 1ml ethylene glycol) adding 30ml fully stirs and seals, and put into heating cabinet, temperature is set as 220 DEG C, dries 48h.Washed by the product acetone obtained, suction filtration is dried.Its composition of analysis of components meets NaNiSO 4f, XRD test analysis is three mutually pure monoclinic phases, and P1 space group, class is as Fig. 4, Fig. 5.
7. claim 2.7008gNaF fully to grind until powder becomes flowing water shape fine and smooth in agate mortar, then add 7.9999gFeSO 4h 2o and 2.0362gCOSO 4h 2o, with acetone as the abundant ground and mixed of medium, acetone of rushing is moved in reactor, and the tetraethylene glycol mixed system (1ml glycerol and 1ml ethylene glycol) adding 30ml fully stirs and seals, and put into heating cabinet, temperature is set as 220 DEG C, dries 48h.Washed by the product acetone obtained, suction filtration is dried.The new material that analysis of components obtains meets NaFe 0.8cO 0.2sO 4f forms.XRD test analysis is three mutually pure monoclinic phases, and P1 space group, class is as Fig. 4, Fig. 5.
8. claim 2.7008gNaF fully to grind until powder becomes flowing water shape fine and smooth in agate mortar, then add 5.9999gFeSO 4h 2o and 4.0724gCOSO 4h 2o, with acetone as the abundant ground and mixed of medium, acetone of rushing is moved in reactor, and the tetraethylene glycol mixed system (1ml glycerol and 1ml ethylene glycol) adding 30ml fully stirs and seals, and put into heating cabinet, temperature is set as 220 DEG C, dries 48h.Washed by the product acetone obtained, suction filtration is dried.The new material analysis of components obtained like this meets NaFe 0.6cO 0.4sO 4f forms.XRD test analysis is three mutually pure monoclinic phases, and P1 space group, class is as Fig. 4, Fig. 5.
9. claim 2.7008gNaF fully to grind until powder becomes flowing water shape fine and smooth in agate mortar, then add 4.9999gFeSO 4h 2o and 5.0905gCOSO 4h 2o, with acetone as the abundant ground and mixed of medium, acetone of rushing is moved in reactor, and the tetraethylene glycol mixed system (1ml glycerol and 1ml ethylene glycol) adding 30ml fully stirs and seals, and put into heating cabinet, temperature is set as 220 DEG C, dries 48h.Washed by the product acetone obtained, suction filtration is dried.The new material that analysis of components obtains meets NaFe 0.5cO 0.5sO 4f forms.XRD test analysis is three mutually pure monoclinic phases, and P1 space group, class is as Fig. 4, Fig. 5.
10. claim 2.7008gNaF fully to grind until powder becomes flowing water shape fine and smooth in agate mortar, then add 7.9999gFeSO 4h 2o and 2.0314gNiSO 4h 2o, with acetone as the abundant ground and mixed of medium, acetone of rushing is moved in reactor, and the tetraethylene glycol mixed system (1ml glycerol and 1ml ethylene glycol) adding 30ml fully stirs and seals, and put into heating cabinet, temperature is set as 220 DEG C, dries 48h.Washed by the product acetone obtained, suction filtration is dried.The new material that analysis of components obtains meets NaFe 0.8ni 0.2sO 4f forms.XRD test analysis is three mutually pure monoclinic phases, and P1 space group, class is as Fig. 4, Fig. 5.
11. claim 2.7008gNaF fully to grind until powder becomes flowing water shape fine and smooth in agate mortar, then add 5.9999gFeSO 4h 2o and 4.0628gNiSO 4h 2o, with acetone as the abundant ground and mixed of medium, acetone of rushing is moved in reactor, and the tetraethylene glycol mixed system (1ml glycerol and 1ml ethylene glycol) adding 30ml fully stirs and seals, and put into heating cabinet, temperature is set as 220 DEG C, dries 48h.Washed by the product acetone obtained, suction filtration is dried.The new material that analysis of components obtains meets NaFe 0.6ni 0.4sO 4f forms.XRD test analysis is three mutually pure monoclinic phases, and P1 space group, class is as Fig. 4, Fig. 5.
12. claim 2.7008gNaF fully to grind until powder becomes flowing water shape fine and smooth in agate mortar, then add 4.9999gFeSO 4h 2o and 5.0785gNiSO 4h 2o, with acetone as the abundant ground and mixed of medium, acetone of rushing is moved in reactor, and the tetraethylene glycol mixed system (1ml glycerol and 1ml ethylene glycol) adding 30ml fully stirs and seals, and put into heating cabinet, temperature is set as 220 DEG C, dries 48h.Washed by the product acetone obtained, suction filtration is dried.The new material that analysis of components obtains like this meets NaFe 0.5ni 0.5sO 4f forms.XRD test analysis is three mutually pure monoclinic phases, and P1 space group, class is as Fig. 4, Fig. 5.

Claims (3)

1. a sodium ion conductor, sodion solid electrolytes and sodium-ion battery positive material iron system fluorosulfuric acid sodium compound NaFe 1-xm xsO 4f, M=Co, Ni, the preparation method of 0≤x≤1, is characterized in that adopting tetraethylene glycol mixed system to make solvent, by monoclinic phase presoma FeSO that is bulk, porous 4h 2o and NiSO 4h 2o or CoSO 4h 2o, mixing and NaF are placed in reactor and carry out solvent thermal reaction in proportion.
2. iron system fluorosulfuric acid sodium compound NaFe as claimed in claim 1 1-xm xsO 4f, M=Co, Ni, the preparation method of 0≤x≤1, is characterized in that tetraethylene glycol mixed system solvent is tetraethylene glycol and glycerol, ethylene glycol or both constitute jointly, and glycerol, ethylene glycol or glycerol and combining of ethylene glycol add in the ratio of mixed solvent cumulative volume 3%-15%.
3. iron system fluorosulfuric acid sodium compound NaFe as claimed in claim 1 1-xm xsO 4f, M=Co, Ni, the preparation method of 0≤x≤1, wherein the monoclinic phase presoma FeSO of bulk, porous 4h 2the preparation of O is by FeSO 47H 2o and sodium hydrosulfite are mixed in 150 DEG C baking oven vacuum dehydrations 3 hour in mass ratio at 3: 1-5: 1, must contain FeSO 4h 2the mixture of O, mixture absolute methanol refluxes as medium.
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