CN103078111A - Preparation methods of monoclinic-phase FeSO4.H2O and triclinic-phase NaFe1-xMxSO4F (M=Co, Ni) - Google Patents

Preparation methods of monoclinic-phase FeSO4.H2O and triclinic-phase NaFe1-xMxSO4F (M=Co, Ni) Download PDF

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CN103078111A
CN103078111A CN2011103288623A CN201110328862A CN103078111A CN 103078111 A CN103078111 A CN 103078111A CN 2011103288623 A CN2011103288623 A CN 2011103288623A CN 201110328862 A CN201110328862 A CN 201110328862A CN 103078111 A CN103078111 A CN 103078111A
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phase
acetone
monoclinic
space group
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CN103078111B (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

The invention provides a preparation method of triclinic-phase NaFe1-xMxSO4F (M=Co, Ni; x=0-1.0). A bulky and porous monoclinic-phase precursor FeSO4.H2O preparation method comprises the steps that: FeSO4.7H2O is sufficiently mixed with insurance powder, and the mixture is heated and dehydrated; and the product is subjected to anhydrous methanol reflux, such that FeSO4.H2O is prepared. The prepared FeSO4.H2O is mixed with MSO4.H2O (M=Co, Ni), and the mixture is subjected to a solvothermal reaction with a chemical dose of NaF, such that a target product NaFe1-xMxSO4F (M is Co or Ni; and x=0-1.0) is prepared. The structure is a triclinic phase, and the structure belongs to a 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 a kind of novel polyanionic compound sodium ion conductor, sodion solid electrolytes and sodium-ion battery electrode anode material preparation method.
[summary of the invention]
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 4Have topological relation by the phase principle of similitude between the 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 the metastable phase polyanionic compound, is because they can be regarded as by Na +, Fe 2+, M 2+(M=Co, Ni), O 2-The NaO that forms 6, FeO 6, MO 6(M=Co, Ni) octahedra anion and SO 4The tetrahedron anion is at F -Under existing, employing altogether nonadjacent oxygen atom connects into the structure with three-dimensional tunnel according to certain orientation, and this tunnel structure is suitable for Na +, Li +Deng alkali ion movement, thereby 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 facet, especially as sodium-ion battery electrode anode material.The present invention includes two parts, a part is FeSO 47H 2The O dehydration generates monoclinic phase presoma FeSO bulk, porous 4H 2O, a part is the FeSO that makes 4H 2O and MSO 4H 2The NaF that O (M=Co, Ni) mixes with chemical dose again makes target product NaFe by solvent thermal reaction 1-xM xSO 4F (M=Co, Ni; X=0-1.0).
Preparation target product NaFe 1-xM xSO 4F (M=Co, Ni; X=0-1.0) presoma is required: the one, pure monoclinic phase FeSO 4H 2O, the 2nd, particle diameter is little and bulk, porous.FeSO 47H 2The O dehydration generates monoclinic phase presoma method bulk, porous to be had: 1. heated 1 hour in 200 ℃ of vacuum; 2. under the atmosphere of nitrogen and hydrogen, 100 ℃ were heated 3 hours.The shortcoming of these two kinds of methods: the former because temperature is higher, can make FeSO owing to be 200 ℃ of heating in vacuum 4H 2The O caking, the presoma that obtains is fluffy not, and the latter can make dehydration not thorough because temperature is low, and atmosphere is complicated, the control trouble.The present invention makes FeSO in order to reach 4H 2O is bulk, porous, prevents oxidation, adopts sodium hydrosulfite auxiliary heating dewatering, because the oxygen consumed solid/liquid/gas reactions occurs in sodium hydrosulfite easily:
2S 2O 4 2-+ O 2+ 4OH -→ 4SO 3 2-+ 2H 2So O can effectively prevent FeSO 4Oxidation occurs, and unnecessary sodium hydrosulfite is soluble in absolute methanol, and backflow can be removed sodium hydrosulfite, drives the monoclinic phase presoma that just obtains satisfactory bulk, porous behind the absolute methanol away.Its method is simple, effective.The synthetic solvent-thermal method of using of target product, the following reaction of foundation:
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; X=0-1.0)
The preparation method: experimentation of the present invention fully grinds for taking by weighing NaF, until powder becomes the flowing water shape fine and smooth, adds the monoclinic phase presoma FeSO of bulk, the porous of corresponding mol ratio again 4H 2O (or FeSO 4H 2O and MSO4H 2The compound of O), as the abundant ground and mixed of medium, the acetone of rushing is moved in the reactor with acetone, the tetraethylene glycol and the mixed system (a small amount of glycerol and ethylene glycol) thereof that add fully stir and seal, put into heating cabinet, Temperature Setting is 220 ℃, baking 48h.The product that obtains is washed with acetone, and the suction filtration oven dry namely obtains NaFeSO 4F (or NaFe 1-xM xSO 4F).In tetraethylene glycol, add the effect that a small amount of polyalcohol can play suction, promote the process of reaction, can also improve pattern, so that size is more even more reasonable.
Sodium-ion battery is to be another best, up-to-date selection for rechargeable battery, although Li-Ion rechargeable battery has good charge storage ability, but owing to expensive the restriction produced in a large number and used, thereby be expected to allow the sodium ion rechargeable battery become alternative lithium ion battery, be used for large scale storage electric energy, cheap new way.The preparation method of the sodium-ion battery of invention is the hot method of ion before, but system is complicated, expensive, and synthesis temperature is higher, 300 ℃, also is difficult to mutually pure.NaFePO wherein 4Own poorly conductive (the electronic and ionic mobility is low), its nanometer or carbon coated could actually be used, meaning is synthetic by high temperature solid-state, this just is difficult to reach character and the structure of manual control, so increased complexity and the cost of technique, the more important thing is that it also fails to satisfy fail safe and practicality problem comprehensively.In October, 2010 reported first such as Rejesh Tripathi new sodium ion positive electrode NaFeSO 4F.It adopts solvent-thermal method preparation, the sodium ion positive electrode NaFeSO that the method makes 4F is for NaFePO before 4Positive electrode is a very large leap.NaFePO 4Or NaFe 1-xM xSO 4F is a kind of metastable phase, and its good conductivity does not need carbon coated just can use, and just can synthesize at low temperatures, so its structure, the fine control of character energy.
The invention process process is divided into:
1. with FeSO 47H 2O and sodium hydrosulfite 3: 1 in mass ratio---evenly mixes at 5: 1 be placed on put into 150 ℃ of baking oven vacuum dehydrations bakings 3 hours in the crucible must FeSO 4H 2The mixture of O and sodium hydrosulfite.
2. with absolute methanol mixture is refluxed and obtain monoclinic phase intermediate FeSO mutually pure, bulk, porous 4H 2O.
3. being 1: 1.1 by Fe and Na atomic ratio,---taking by weighing NaF at 1: 1.2 fully grinds, until powder becomes the flowing water shape fine and smooth, is 1: 1.1 by Fe and Na atomic ratio again---adds FeSO at 1: 1.2 4H 2O, as the abundant ground and mixed of medium, the acetone of rushing is moved in the reactor with acetone, the tetraethylene glycol mixed system (glycerol of the 3%-15% of volume and ethylene glycol) that adds 30ml fully stirs and seals, put into heating cabinet, Temperature Setting is 220 ℃, baking 48h.The product that obtains is washed the suction filtration oven dry with acetone.
4. in special reactor, be to take by weighing FeSO at 1: 1.1 by Fe and Na atomic ratio 4H 2O and NaF, add an amount of tetraethylene glycol mixed system (glycerol of the 3%-15% of volume and ethylene glycol) and zirconium ball, tighten reactor and place sample pulverizer, put into 220 ℃ of baking oven baking 48h. behind the ball milling 12h-16h and the product that obtains is washed the suction filtration oven dry with acetone.
5. take by weighing an amount of COSO 47H 2O is placed in 150 ℃ baking oven vacuum dehydration baking and obtained monoclinic phase presoma COSO bulk, porous in 3 hours in crucible 4H 2O.
6. take by weighing an amount of NiSO 46H 2O is placed in 200 ℃ baking oven vacuum dehydration baking and obtained monoclinic phase presoma NiSO bulk, porous in 3 hours in crucible 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 2The O mixture substitutes FeSO in the 3rd step 4H 2O, the product that obtains are NaFe 1-xM xSO 4F (M=Co, Ni; X=0-1.0).
Advantage of the present invention is:
1. novel sodium ion positive electrode NaFeSO 4F or NaFe 1-xM xSO 4F (M=Co, Ni; X=0-1.0) good conductivity does not need carbon coated just can use, and just can synthesize at low temperatures, is metastable phase, so the fine control of its structural property.
2. the FeSO for preparing 4H 2O is bulk, porous, and is mutually pure, and the sodium hydrosulfite low price is easy to use.
3. equipment is simple, and suitable for mass production is used.
Description of drawings
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 mix puts into crucible, places 150 ℃ of baking oven vacuum dehydration bakings to get FeSO in 3 hours 4H 2The mixture of O and sodium hydrosulfite, color are the mixture of grey black.Take by weighing the 6g mixture and pour in the 250ml flask, adding 200ml absolute methanol is placed on and carries out back flow reaction (jacket temperature is set as 68 ℃) on the heating collar.Every mistake was changed once new absolute methanol in 20 minutes, and each 200ml changes clothes 4 times.Add at last the acetone suction filtration, in 100 ℃ of baking ovens, dry.XRD figure visible structure is pure monoclinic phase, C2/C space group, sees Fig. 1.
2. claim 20gFeSO 47H 2O and 5g sodium hydrosulfite mix puts into crucible, places 150 ℃ of baking oven vacuum dehydration bakings to get FeSO in 3 hours 4H 2The mixture of O and sodium hydrosulfite, color are the mixture of grey black.Take by weighing the 6g mixture and pour in the 250ml flask, adding 200ml absolute methanol is placed on and carries out back flow reaction (the water-bath Temperature Setting is 70 ℃) in the water-bath.Every mistake was changed once new absolute methanol in 20 minutes, and each 200ml changes clothes 4 times.Add at last the acetone suction filtration, in 100 ℃ of baking ovens, dry.XRD figure visible structure is pure monoclinic phase, C2/C space group, class such as Fig. 1.
3. claim 30gFeSO 47H 2O and 10g sodium hydrosulfite mix puts into crucible, places 150 ℃ of baking oven vacuum dehydration bakings to get FeSO in 3 hours 4H 2The mixture of O and sodium hydrosulfite.Color is the mixture of grey black.Take by weighing the 6g intermediate and pour in the 250ml flask, adding 200ml absolute methanol is placed on and carries out back flow reaction (the water-bath Temperature Setting is 70 ℃) in the water-bath.Every mistake was changed once new absolute methanol in 20 minutes, and each 200ml changes clothes 4 times, until sodium hydrosulfite is cleaned.Add at last the acetone suction filtration, in 100 ℃ of baking ovens, dry.XRD figure visible structure is pure monoclinic phase, C2/C space group, class such as Fig. 1.
4. claim 25gFeSO 47H 2O and 5g sodium hydrosulfite mix puts into crucible, places 150 ℃ of baking oven vacuum dehydration bakings to get FeSO in 3 hours 4H 2The intermediate of O and sodium hydrosulfite.Its irregular colour is even, the grey black that has, and the lime that has has caking phenomenon.Take by weighing the 6g intermediate and pour in the 250ml flask, adding 200ml absolute methanol is placed on and carries out back flow reaction (the water-bath Temperature Setting is 70 ℃) in the water-bath.Every mistake was changed once new absolute methanol in 20 minutes, and each 200ml changes clothes 3-4 time, until sodium hydrosulfite is cleaned.Add at last the acetone suction filtration, in 100 ℃ of baking ovens, dry.XRD figure visible structure is pure monoclinic phase, C2/C space group, class such as Fig. 1.
5. claim 25g COSO 47H 2O is placed in 150 ℃ baking oven vacuum dehydration baking and obtained monoclinic phase presoma COSO bulk, porous in 3 hours in crucible 4H 2O.XRD figure visible structure is pure monoclinic phase, C2/C space group, sees Fig. 2.
6. claim 28gNiSO 46H 2O is placed in 200 ℃ baking oven vacuum dehydration baking and obtained monoclinic phase presoma NiSO bulk, porous in 3 hours in crucible 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; X=0-1.0) preparation method
1. claim that 2.7090gNaF fully grinds until powder becomes the flowing water shape fine and smooth in agate mortar, add again 9.9921gFeSO 4H 2O, as the abundant ground and mixed of medium, the acetone of rushing is moved in the reactor with acetone, and the tetraethylene glycol mixed system (0.5ml glycerol and 0.5ml ethylene glycol) that adds 30ml fully stirs and seals, and puts into heating cabinet, and Temperature Setting is 220 ℃, baking 48h.The product that obtains is washed the suction filtration oven dry with acetone.Its composition of constituent analysis meets NaFeSO 4The SEM figure of F, the XRD test analysis is three mutually pure monoclinic phases, the P1 space group is seen Fig. 4, Fig. 5.
2. claim that 2.7361gNaF fully grinds until powder becomes the flowing water shape fine and smooth in agate mortar, add again 10.069gFeSO 4H 2O, as the abundant ground and mixed of medium, the acetone of rushing is moved in the reactor with acetone, and the tetraethylene glycol mixed system (1ml glycerol and 1ml ethylene glycol) that adds 30ml fully stirs and seals, and puts into heating cabinet, and Temperature Setting is 220 ℃, baking 48h.The product that obtains is washed the suction filtration oven dry with acetone.Its composition of constituent analysis meets NaFeSO 4F, XRD test analysis are three mutually pure monoclinic phases, and the P1 space group is such as Fig. 4, Fig. 5.
3. claim that 2.7233gNaF fully grinds until powder becomes the flowing water shape fine and smooth in agate mortar, add again 10.022gFeSO 4H 2O, as the abundant ground and mixed of medium, the acetone of rushing is moved in the reactor with acetone, and the tetraethylene glycol mixed system (2ml glycerol and 2ml ethylene glycol) that adds 30ml fully stirs and seals, and puts into heating cabinet, and Temperature Setting is 220 ℃, baking 48h.The product that obtains is washed the suction filtration oven dry with acetone.Its composition of constituent analysis meets NaFeSO 4F, XRD test analysis are three mutually pure monoclinic phases, and the P1 space group is such as Fig. 4, Fig. 5.
4. take by weighing 9.9958g presoma FeSO 4H 2O and 2.7215gNaF add 30ml tetraethylene glycol and 170g zirconium ball in special reactor, tighten reactor and place on the sample pulverizer, put into 220 ℃ of baking oven baking 48h. behind the ball milling 12h and the product that obtains are washed the suction filtration oven dry with acetone.Its composition of constituent analysis meets NaFeSO 4F, XRD test analysis are three mutually pure monoclinic phases, and the P1 space group is such as Fig. 4, Fig. 5.
5. claim that 2.4318gNaF fully grinds until powder becomes the flowing water shape fine and smooth in agate mortar, add again 10.0070gCOSO 4H 2O, as the abundant ground and mixed of medium, the acetone of rushing is moved in the reactor with acetone, and the tetraethylene glycol mixed system (1ml glycerol and 1ml ethylene glycol) that adds 30ml fully stirs and seals, and puts into heating cabinet, and Temperature Setting is 220 ℃, baking 48h.The product that obtains being washed the suction filtration oven dry with acetone. its composition of constituent analysis meets NaCoSO 4F, XRD test analysis are three mutually pure monoclinic phases, P1 space group, class such as Fig. 4, Fig. 5.
6. claim that 2.6822gNaF fully grinds until powder becomes the flowing water shape fine and smooth in agate mortar, add again 10.0007gNiSO 4H 2O, as the abundant ground and mixed of medium, the acetone of rushing is moved in the reactor with acetone, and the tetraethylene glycol mixed system (1ml glycerol and 1ml ethylene glycol) that adds 30ml fully stirs and seals, and puts into heating cabinet, and Temperature Setting is 220 ℃, baking 48h.The product that obtains is washed the suction filtration oven dry with acetone.Its composition of constituent analysis meets NaNiSO 4F, XRD test analysis are three mutually pure monoclinic phases, P1 space group, class such as Fig. 4, Fig. 5.
7. claim 2.7008gNaF in agate mortar, fully grinding until powder becomes the flowing water shape fine and smooth, add again 7.9999gFeSO 4H 2O and 2.0362gCOSO 4H 2O, as the abundant ground and mixed of medium, the acetone of rushing is moved in the reactor with acetone, and the tetraethylene glycol mixed system (1ml glycerol and 1ml ethylene glycol) that adds 30ml fully stirs and seals, and puts into heating cabinet, and Temperature Setting is 220 ℃, baking 48h.The product that obtains is washed the suction filtration oven dry with acetone.The new material that constituent analysis obtains meets NaFe 0.8CO 0.2SO 4F forms.The XRD test analysis is three mutually pure monoclinic phases, P1 space group, class such as Fig. 4, Fig. 5.
8. claim 2.7008gNaF in agate mortar, fully grinding until powder becomes the flowing water shape fine and smooth, add again 5.9999gFeSO 4H 2O and 4.0724gCOSO 4H 2O, as the abundant ground and mixed of medium, the acetone of rushing is moved in the reactor with acetone, and the tetraethylene glycol mixed system (1ml glycerol and 1ml ethylene glycol) that adds 30ml fully stirs and seals, and puts into heating cabinet, and Temperature Setting is 220 ℃, baking 48h.The product that obtains is washed the suction filtration oven dry with acetone.The new material constituent analysis that obtains like this meets NaFe 0.6CO 0.4SO 4F forms.The XRD test analysis is three mutually pure monoclinic phases, P1 space group, class such as Fig. 4, Fig. 5.
9. claim 2.7008gNaF in agate mortar, fully grinding until powder becomes the flowing water shape fine and smooth, add again 4.9999gFeSO 4H 2O and 5.0905gCOSO 4H 2O, as the abundant ground and mixed of medium, the acetone of rushing is moved in the reactor with acetone, and the tetraethylene glycol mixed system (1ml glycerol and 1ml ethylene glycol) that adds 30ml fully stirs and seals, and puts into heating cabinet, and Temperature Setting is 220 ℃, baking 48h.The product that obtains is washed the suction filtration oven dry with acetone.The new material that constituent analysis obtains meets NaFe 0.5CO 0.5SO 4F forms.The XRD test analysis is three mutually pure monoclinic phases, P1 space group, class such as Fig. 4, Fig. 5.
10. claim 2.7008gNaF in agate mortar, fully grinding until powder becomes the flowing water shape fine and smooth, add again 7.9999gFeSO 4H 2O and 2.0314gNiSO 4H 2O, as the abundant ground and mixed of medium, the acetone of rushing is moved in the reactor with acetone, and the tetraethylene glycol mixed system (1ml glycerol and 1ml ethylene glycol) that adds 30ml fully stirs and seals, and puts into heating cabinet, and Temperature Setting is 220 ℃, baking 48h.The product that obtains is washed the suction filtration oven dry with acetone.The new material that constituent analysis obtains meets NaFe 0.8Ni 0.2SO 4F forms.The XRD test analysis is three mutually pure monoclinic phases, P1 space group, class such as Fig. 4, Fig. 5.
11. claim 2.7008gNaF in agate mortar, fully grinding until powder becomes the flowing water shape fine and smooth, add again 5.9999gFeSO 4H 2O and 4.0628gNiSO 4H 2O, as the abundant ground and mixed of medium, the acetone of rushing is moved in the reactor with acetone, and the tetraethylene glycol mixed system (1ml glycerol and 1ml ethylene glycol) that adds 30ml fully stirs and seals, and puts into heating cabinet, and Temperature Setting is 220 ℃, baking 48h.The product that obtains is washed the suction filtration oven dry with acetone.The new material that constituent analysis obtains meets NaFe 0.6Ni 0.4SO 4F forms.The XRD test analysis is three mutually pure monoclinic phases, P1 space group, class such as Fig. 4, Fig. 5.
12. claim 2.7008gNaF in agate mortar, fully grinding until powder becomes the flowing water shape fine and smooth, add again 4.9999gFeSO 4H 2O and 5.0785gNiSO 4H 2O, as the abundant ground and mixed of medium, the acetone of rushing is moved in the reactor with acetone, and the tetraethylene glycol mixed system (1ml glycerol and 1ml ethylene glycol) that adds 30ml fully stirs and seals, and puts into heating cabinet, and Temperature Setting is 220 ℃, baking 48h.The product that obtains is washed the suction filtration oven dry with acetone.The new material that constituent analysis obtains like this meets NaFe 0.5Ni 0.5SO 4F forms.The XRD test analysis is three mutually pure monoclinic phases, P1 space group, class such as Fig. 4, Fig. 5.

Claims (4)

1. a sodium ion conductor, sodion solid electrolytes and sodium-ion battery electrode anode material iron are the fluorosulfuric acid sodium compound, and its general formula is NaFe 1-xM xSO 4F, wherein M=Ni, Co, 0≤X≤1, structure is three monoclinic phases, the P1 space group.
2. iron as claimed in claim 1 is the fluorosulfuric acid sodium compound, and its preparation method adopts the tetraethylene glycol mixed system to make solvent, with monoclinic phase presoma FeSO bulk, porous 4H 2O and NiSO 4H 2O or CoSO 4H 2O mixes in proportion and NaF places reactor to carry out solvent thermal reaction.
3. tetraethylene glycol mixed system solvent as claimed in claim 2 is tetraethylene glycol and glycerol, ethylene glycol or the two associating, and by volume 3%-15% mixes the dicyandiamide solution that forms.
4. bulk, the monoclinic phase of porous as claimed in claim 2, C2/C space group presoma FeSO 4H 2O, its preparation method are with FeSO 47H 2O and sodium hydrosulfite are mixed in 150 ℃ of baking oven vacuum dehydrations must contain FeSO 4H 2The mixture of O, mixture refluxes as medium with absolute methanol.
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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
CN109867308A (en) * 2017-12-04 2019-06-11 中国科学院大连化学物理研究所 A kind of K2Fe3(SO4)3(OH)2Compound and its preparation and application
WO2021114401A1 (en) * 2019-12-09 2021-06-17 苏州大学 Iron-based sodium ion battery positive material, manufacturing method therefor, and sodium ion full battery

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN109867308A (en) * 2017-12-04 2019-06-11 中国科学院大连化学物理研究所 A kind of K2Fe3(SO4)3(OH)2Compound and its preparation and application
WO2021114401A1 (en) * 2019-12-09 2021-06-17 苏州大学 Iron-based sodium ion battery positive material, manufacturing method therefor, and sodium ion full battery

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