CN101935072B - Ferrous lithium sulphate fluoride as well as preparation method and application thereof - Google Patents

Ferrous lithium sulphate fluoride as well as preparation method and application thereof Download PDF

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CN101935072B
CN101935072B CN201010263949.2A CN201010263949A CN101935072B CN 101935072 B CN101935072 B CN 101935072B CN 201010263949 A CN201010263949 A CN 201010263949A CN 101935072 B CN101935072 B CN 101935072B
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lithium
acid ferrous
fluorosulfuric acid
ferrous lithium
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郭玉国
郭维
万立骏
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Institute of Chemistry CAS
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Abstract

The invention discloses ferrous lithium sulphate fluoride as cathode materials of lithium batteries as well as a preparation method and application thereof. The ferrous sulphate lithium fluoride is prepared according to the following steps of: adding FeSO4.xH2O, LiF and a solvent into a reaction container and mixing the added substances to obtain a reaction solution, and heating the reaction solution to 200-350 DEG C for reaction to obtain the ferrous sulphate fluoride, wherein x in the FeSO4.xH2O is an integer greater than or equal to 0, and the solvent is alcohol or polyethylene glycol containing at least one hydroxide radical. In the invention, the preparation method is simple and the raw materials are rich and easy to obtain; thus, the preparation method is suitable for mass production and has high practicality degree. In addition the obtained ferrous lithium sulphate fluoride is in nanoparticles with high actual capacity and can be directly used as cathode materials of lithium-ion batteries.

Description

Fluorosulfuric acid ferrous lithium and preparation method thereof and application
Technical field
The present invention relates to a kind of fluorosulfuric acid ferrous lithium and preparation method thereof and application.
Background technology
Along with the widespread use of lithium ion battery in portable type electronic product, electromobile and instant-plugging hybrid electric vehicle, to anode material for lithium-ion batteries (as LiCoO 2, LiMn 2o 4, LiFePO 4) and the research of negative material (as C, Sn, Si) day by day deep.With respect to negative material, the research of positive electrode material relatively lags behind.As business-like LiCoO 2the problems such as existence and stability, cost and environment.LiFePO 4because of cheap, aboundresources and non-environmental-pollution problem, moderate voltage platform and the higher advantages such as capacity become the focus of exploitation.But LiFePO 4poorly conductive, has limited making full use of of its active material, need to carry out carbon to it and be coated or doping vario-property.The novel LiMSO of report one class such as M.Armand in 2009 4f (M=3d metal) material, wherein fluorosulfuric acid ferrous lithium (LiFeSO 4f) present excellent chemical property.LiFeSO 4the charge and discharge platform 3.6V of F, a little more than LiFePO 4charge and discharge platform, theoretical capacity 151mAh/g, a little less than LiFePO 4.But LiFeSO 4the ion of F and electronic conduction performance are better than LiFePO 4, be conducive to improve the performance of lithium ion battery.Therefore, LiFeSO 4f is considered to the Olivine-type Cathode Material in Li-ion Batteries that the utmost point has application potential.But need to adopt ionic liquid as solvent in the preparation process of having reported, severe reaction conditions, to having relatively high expectations of equipment, is unfavorable for scale operation, its competitive edge and application have widely been limited.
Summary of the invention
The object of this invention is to provide a kind of anode material for lithium-ion batteries fluorosulfuric acid ferrous lithium and preparation method thereof.
Fluorosulfuric acid ferrous lithium provided by the present invention is to prepare according to the method comprising the steps: in reaction vessel, add FeSO 4xH 2o, LiF and solvent, mix, and obtains reaction soln; Again described reaction soln is heated to 200-350 ℃ and reacts, obtain described fluorosulfuric acid ferrous; Wherein, described FeSO 4xH 2x in O is more than or equal to 0 integer, and described solvent is alcohol or the polyoxyethylene glycol that contains at least one hydroxyl.
In the present invention, described FeSO 4xH 2o specifically can be following any one: FeSO 4, FeSO 4h 2o, FeSO 44H 2o and FeSO 47H 2o.
The described alcohol that contains at least one hydroxyl is triacontanol price quote, benzhydrol, and glycerol or Tetraglycol 99, be preferably benzhydrol, glycerol or Tetraglycol 99.
The weight-average molecular weight of described polyoxyethylene glycol can be 200-20000, is preferably 200-1000.
FeSO in described reaction soln 4xH 2the mol ratio of O and LiF can be 1: 1-1.5, is preferably 1: 1-1.2.
The reaction times of described reaction can be 1-72h, preferably 5-60h.
The prepared fluorosulfuric acid ferrous lithium of the present invention exists with the form of fluorosulfuric acid ferrous lithium particle, and the particle diameter of described fluorosulfuric acid ferrous lithium particle can be 10nm-2 μ m.
Further object of the present invention is to provide the application of described fluorosulfuric acid ferrous lithium.
Application provided by the present invention is that fluorosulfuric acid ferrous lithium is as the application of battery electrode material, particularly as the application of anode material for lithium-ion batteries.
The present invention also provides a kind of energy storage elements, and described energy storage elements contains described fluorosulfuric acid ferrous lithium, this energy storage elements preferred lithium ionization cell.
The present invention also provides a kind of portable electric appts, and this electronics uses above-mentioned energy storage elements, the preferred mobile telephone of this portable electric appts, photographic camera, pick up camera, MP3, MP4, notebook computer.
Compared with prior art, the method for preparing fluorosulfuric acid ferrous lithium provided by the invention is simple, and raw material is easy to get, suitable for mass production, and degree of being practical is high.And the fluorosulfuric acid ferrous lithium obtaining is nano material, can be directly as the electrode materials of battery, use.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) figure of the fluorosulfuric acid ferrous lithium of embodiment 1 preparation.
Fig. 2 is the fluorosulfuric acid ferrous lithium electron scanning micrograph of embodiment 1 preparation.
Fig. 3 is charging and discharging curve when fluorosulfuric acid ferrous lithium is as anode material for lithium-ion batteries in embodiment 1.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, all can obtain from commercial channels.
Embodiment 1, prepare fluorosulfuric acid ferrous lithium
Press FeSO 4h 2o: LiF=1: 1.1 mol ratio takes, adds Tetraglycol 99 as solvent, mixes.At 300 ℃, react 5h.React complete, separated dry, obtain pulverulent solids.
With powder x-ray diffraction (Rigaku DmaxrB, CuK αray) furanone structure.Result as shown in Figure 1.As can be seen from the figure, in spectrogram, there is not impurity peaks, illustrate that product purity is high.
By scanning electronic microscope (JEOL-6700F), characterized the pattern of fluorosulfuric acid ferrous lithium, as shown in Figure 2.As seen from the figure, the grain diameter scope of this material is 20-200nm, as the particle diameter indicating in the figure particle that is 159.4nm and the particle diameter particle that is 71.7nm.
The Electrochemical Characterization of fluorosulfuric acid ferrous lithium:
The fluorosulfuric acid ferrous lithium, carbon black and the binding agent that prepare are mixed and are made into slurry with mass ratio at 70: 20: 10, be coated to equably and in aluminum foil current collector, obtain working electrode, using lithium sheet metal as to electrode, glass fibre membrane (Britain Whatman company) is as barrier film, 1mol/L LiPF 6(solvent is the volume ratio NSC 11801 of 1: 1 and methylcarbonate mixed solution), as electrolytic solution, in glove box, assembling obtains Swagelok type battery.
The battery of above-mentioned assembling is carried out to charge-discharge test on LAND charge-discharge test instrument, and the interval that discharges and recharges of test is 4.2-2.5V.
As shown in Figure 3, synthetic fluorosulfuric acid ferrous lithium has good charging and discharging curve to result.Visible, when the synthetic fluorosulfuric acid ferrous lithium of the present invention is used as anode material for lithium-ion batteries, there is chemical property.The fluorosulfuric acid ferrous lithium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Embodiment 2, prepare fluorosulfuric acid ferrous lithium
Press FeSO 4h 2o: LiF=1: 1.15 mol ratio takes, adds glycerol as solvent, mixes.At 285 ℃, react 36h.Complete, separated dry, obtain pulverulent solids.The fluorosulfuric acid ferrous lithium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Embodiment 3, prepare fluorosulfuric acid ferrous lithium
Press FeSO 4h 2o: LiF=1: 1.2 mol ratio takes, adds polyoxyethylene glycol (weight-average molecular weight is 200) as solvent, to mix.At 250 ℃, react 60h.Complete, separated dry, obtain pulverulent solids.The fluorosulfuric acid ferrous lithium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Embodiment 4, prepare fluorosulfuric acid ferrous lithium
Press FeSO 4h 2o: LiF=1: 1.2 mol ratio takes, adds polyoxyethylene glycol (weight-average molecular weight is 300) as solvent, to mix.At 310 ℃, react 12h.Complete, separated dry, obtain pulverulent solids.The fluorosulfuric acid ferrous lithium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Embodiment 5, prepare fluorosulfuric acid ferrous lithium
Press FeSO 4h 2o: LiF=1: 1.15 mol ratio takes, adds polyoxyethylene glycol (weight-average molecular weight is 400) as solvent, to mix.At 340 ℃, react 2h.Complete, separated dry, obtain pulverulent solids.The fluorosulfuric acid ferrous lithium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Embodiment 6, prepare fluorosulfuric acid ferrous lithium
Press FeSO 44H 2o: LiF=1: 1.05 mol ratio takes, adds Tetraglycol 99 as solvent, mixes.At 320 ℃, react 24h.Complete, separated dry, obtain pulverulent solids.The fluorosulfuric acid ferrous lithium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Embodiment 7, prepare fluorosulfuric acid ferrous lithium
Press FeSO 44H 2o: LiF=1: 1 mol ratio takes, adds glycerol as solvent, mixes.At 285 ℃, react 60h.Complete, separated dry, obtain pulverulent solids.The fluorosulfuric acid ferrous lithium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Embodiment 8, prepare fluorosulfuric acid ferrous lithium
Press FeSO 44H 2o: LiF=1: 1.3 mol ratio takes, adds polyoxyethylene glycol (weight-average molecular weight is 200) as solvent, to mix.At 220 ℃, react 72h.Complete, separated dry, obtain pulverulent solids.The fluorosulfuric acid ferrous lithium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Embodiment 9, prepare fluorosulfuric acid ferrous lithium
Press FeSO 44H 2o: LiF=1: 1.2 mol ratio takes, adds polyoxyethylene glycol (weight-average molecular weight is 300) as solvent, to mix.At 280 ℃, react 36h.Complete, separated dry, obtain pulverulent solids.The fluorosulfuric acid ferrous lithium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Embodiment 10, prepare fluorosulfuric acid ferrous lithium
Press FeSO 44H 2o LiF=1: 1.1 mol ratio takes, adds polyoxyethylene glycol (weight-average molecular weight is 20000) as solvent, to mix.At 320 ℃, react 8h.Complete, separated dry, obtain pulverulent solids.The fluorosulfuric acid ferrous lithium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Embodiment 11, prepare fluorosulfuric acid ferrous lithium
Press FeSO 47H 2o: LiF=1: 1.15 mol ratio takes, adds Tetraglycol 99 as solvent, mixes.At 325 ℃, react 12h.Complete, separated dry, obtain pulverulent solids.The fluorosulfuric acid ferrous lithium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Embodiment 12, prepare fluorosulfuric acid ferrous lithium
Press FeSO 47H 2o: LiF=1: 1.5 mol ratio takes, adds glycerol as solvent, mixes.At 290 ℃, react 48h.Complete, separated dry, obtain pulverulent solids.The fluorosulfuric acid ferrous lithium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Embodiment 13, prepare fluorosulfuric acid ferrous lithium
Press FeSO 47H 2o: LiF=1: 1.2 mol ratio takes, adds polyoxyethylene glycol (weight-average molecular weight is 200) as solvent, to mix.At 285 ℃, react 72h.Complete, separated dry, obtain pulverulent solids.The fluorosulfuric acid ferrous lithium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Embodiment 14, prepare fluorosulfuric acid ferrous lithium
Press FeSO 47H 2o: LiF=1: 1.5 mol ratio takes, adds polyoxyethylene glycol (weight-average molecular weight is 300) as solvent, to mix.At 310 ℃, react 12h.Complete, separated dry, obtain pulverulent solids.The fluorosulfuric acid ferrous lithium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Embodiment 15, prepare fluorosulfuric acid ferrous lithium
Press FeSO 47H 2o: LiF=1: 1.15 mol ratio takes, adds polyoxyethylene glycol (weight-average molecular weight is 400) as solvent, to mix.At 300 ℃, react 10h.Complete, separated dry, obtain pulverulent solids.The fluorosulfuric acid ferrous lithium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Embodiment 16, prepare fluorosulfuric acid ferrous lithium
Press FeSO 4: LiF=1: 1.3 mol ratio takes, adds polyoxyethylene glycol (weight-average molecular weight is 400) as solvent, to mix.At 300 ℃, react 18h.Complete, separated dry, obtain pulverulent solids.The fluorosulfuric acid ferrous lithium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Embodiment 17, prepare fluorosulfuric acid ferrous lithium
Press FeSO 44H 2o: LiF=1: 1.2 mol ratio takes, adds polyoxyethylene glycol (weight-average molecular weight is 1000) as solvent, to mix.At 320 ℃, react 8h.Complete, separated dry, obtain pulverulent solids.The fluorosulfuric acid ferrous lithium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Embodiment 18, prepare fluorosulfuric acid ferrous lithium
Press FeSO 4h 2o: LiF=1: 1.15 mol ratio takes, adds benzhydrol as solvent, mixes.At 298 ℃, react 10h.Complete, separated dry, obtain pulverulent solids.The fluorosulfuric acid ferrous lithium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
The preparation condition of table 1, fluorosulfuric acid ferrous lithium material and simulated battery test result
Figure BSA00000247713800061
According to the result of table 1, can find out, alcohol or polyoxyethylene glycol that the present invention be take containing at least one hydroxyl are reaction media, utilize FeSO 4xH 2o is that source of iron and LiF are that fluorosulfuric acid ferrous lithium positive electrode material can be conveniently prepared in lithium source.Utilize the inventive method not only can greatly reduce the preparation cost of material, and the fluorosulfuric acid ferrous lithium positive electrode material that the present invention obtains has all shown higher capacity.

Claims (7)

1. a method of preparing fluorosulfuric acid ferrous lithium, comprises the steps: to add FeSO in reaction vessel 4xH 2o, LiF and solvent, mix, and obtains reaction soln; Again described reaction soln is heated to 200-350 ℃ and reacts, obtain described fluorosulfuric acid ferrous; Wherein, described FeSO 4xH 2x in O is more than or equal to 0 integer, and described solvent is alcohol or the polyoxyethylene glycol that contains at least one hydroxyl;
The described alcohol that contains at least one hydroxyl is triacontanol price quote, benzhydrol, glycerol or Tetraglycol 99; The weight-average molecular weight of described polyoxyethylene glycol is 200-20000.
2. method according to claim 1, is characterized in that: described FeSO 4xH 2o be following any one: FeSO 4, FeSO 4h 2o, FeSO 44H 2o and FeSO 47H 2o.
3. method according to claim 1 and 2, is characterized in that: the weight-average molecular weight of described polyoxyethylene glycol is 200-1000.
4. method according to claim 1 and 2, is characterized in that: FeSO in described reaction soln 4xH 2the mol ratio of O and LiF is 1: 1-1.5.
5. method according to claim 4, is characterized in that: FeSO in described reaction soln 4xH 2the mol ratio of O and LiF is 1: 1-1.2.
6. method according to claim 1 and 2, is characterized in that: the reaction times of described reaction is 1-72h.
7. method according to claim 6, is characterized in that: the reaction times of described reaction is 5-60h.
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CN102332580B (en) * 2011-03-15 2013-11-27 中国科学院物理研究所 Fluorinated ferric sulfate salt compound as well as preparation method and application thereof
TWI442616B (en) * 2011-12-23 2014-06-21 Ind Tech Res Inst Hybrid energy storage device
CN105668643B (en) * 2016-01-11 2018-05-29 华南师范大学 A kind of preparation method of anode material for lithium-ion batteries
CN106853997B (en) * 2016-12-14 2018-02-06 北京理工大学 A kind of positive electrode and preparation method thereof and positive pole coating material and lithium ion battery
CN106876793A (en) * 2017-03-15 2017-06-20 山东威林特新能源科技有限公司 A kind of lithium titanate battery preparation method of high circulation performance
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
CN108054360B (en) * 2017-12-08 2020-04-10 安徽天时新能源科技有限公司 Fluorinated lithium iron sulfate cathode material for low-temperature lithium battery and preparation method thereof

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