CN103400981B - A kind of hexagonal walnut iron lithium silicate aggregation and preparation method thereof - Google Patents

A kind of hexagonal walnut iron lithium silicate aggregation and preparation method thereof Download PDF

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CN103400981B
CN103400981B CN201310277184.1A CN201310277184A CN103400981B CN 103400981 B CN103400981 B CN 103400981B CN 201310277184 A CN201310277184 A CN 201310277184A CN 103400981 B CN103400981 B CN 103400981B
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lithium
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pit shape
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CN103400981A (en
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褚卫国
米麟
王汉夫
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National Center for Nanosccience and Technology China
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Abstract

The present invention relates to a kind of method that hydro thermal method prepares hexagonal walnut iron lithium silicate aggregation positive electrode, preparation process first divalent iron salt and silica dispersions, lithium hydroxide solution is carried out according to a certain percentage in the presence of surfactants mixing, reacting, and finally obtains single-phase ferric metasilicate lithium by hydro-thermal reaction under suitable conditions.The ferric metasilicate lithium aggregation average grain diameter that this method obtains is about 1 μm, and cross section is hexagonal peach-pit shape, and each hexagonal peach-pit shape aggregation is loosely made up of less nano particle.

Description

A kind of hexagonal walnut iron lithium silicate aggregation and preparation method thereof
Technical field
The present invention relates to technical field of energy material preparation, particularly, the present invention relates to a kind of hexagonal walnut iron lithium silicate aggregation and preparation method thereof.
Background technology
Along with various mobile electronic device, the developing rapidly of hybrid electric vehicle, also more and more higher to the requirement of performance of lithium ion battery.Wherein, the performance of anode material for lithium-ion batteries and price are keys of its development of restriction.Since reported first LiFePO4 in 1997 can be used as anode material for lithium-ion batteries, LiFePO4 is subject to extensive concern with its low cost, nontoxic and good security performance.But poor electron conduction but limits its development.Therefore, people constantly explore, and expect the high performance lithium ion battery anode material finding to have better conductivity.And silicate lithium intercalation compound (Li 2mSiO 4, M=Fe, Mn, Co, Ni) and due to the existence of the Si-O key of its uniqueness, its electron conduction is likely better than the LiFePO4 previously found, and theoretical specific capacity is close with LiFePO4 when single electron removal lithium embedded.Therefore, people's extensive concern is subject to.At present, research work mainly still concentrates on the exploration of material synthesis method.What is more important, compared with LiFePO4, when ferric metasilicate lithium deintercalation 2 lithium ions, its theoretical specific capacity is about the twice of LiFePO4.Therefore, the synthesis studying ferric metasilicate lithium has important science and practical significance.
At present, the exemplary manufacturing process of the ferric metasilicate lithium of bibliographical information has high temperature solid-state method, sol-gal process and hydro thermal method etc.High temperature solid-state method: A.Nyten(A.Nyten etc., Electrochemistry Communications7 (2005) 156-160) etc. people by high temperature solid-state method with lithium metasilicate, ferrous oxalate and tetraethoxysilane for raw material, at CO/CO after mixing 2lower 750 DEG C of atmosphere reacts 24h high―temperature nuclei Li 2feSiO 4/ C composite.Hydro thermal method: R.Dominko(R.Dominko etc., Electrochemistry Communications8 (2006) 217-222) etc. people silicon dioxide is dispersed in lithium hydroxide solution through ultrasonic wave added, then mix with solution of ferrous chloride, 150 DEG C of more than isothermal reaction 72h in enclosed high pressure still, the powder obtained uses distilled water cyclic washing under an ar atmosphere, obtains ferric metasilicate lithium powder after drying.Sol-gal process: R.Dominko(R.Dominko, Journal of Power Sources184 (2008) 462-468) etc. to hold be raw material by the mixture of ironic citrate, ferric nitrate, lithium acetate and SiO 2 powder, gel is prepared in ultrasonic water bath, drying, reacts 1h after grinding and obtains ferric metasilicate lithium under the inert atmosphere of 700 DEG C.
In said method, the material grains that high temperature solid phase synthesis obtains and particle greatly, are unfavorable for giving full play to of ferric metasilicate lithium chemical property; And sol-gal process is difficult to control course of reaction and degree, be difficult to obtain single-phase ferric metasilicate lithium.
In addition, CN103078120A discloses a kind of preparation method with the ferrosilicon silicate of lithium anode material for lithium-ion batteries of hierarchical organization, comprise the following steps: in the mixed solvent of Organic Alcohol and distilled water, 1) add molysite and organic acid or organic amine, stirring and being made into iron concentration is 0.0001 ~ 3M solution, Organic Alcohol and distilled water volume proportion are 40:20 ~ 0:60, stand-by; 2) silicon source material and lithium salts are dispersed in distilled water, stir 10 ~ 60 minutes, be made into silicon and lithium concentration is respectively that 0.0001 ~ 3M mixed liquor is stand-by; 3) by the mixed solution of step 1) and step 2) mixed solution mix and blend 10-60 minute loading reactor, its mixing reactant in lithium: iron: silicon mol ratio=2:1:1 ~ 5:1:1; 4) reactor of step 3) is put into hydro-thermal reaction case and react 4-8 days under 180-210 DEG C of hydrothermal condition, products therefrom carries out washing and the dry ferrosilicon silicate of lithium obtaining hierarchical organization, but the method hydro-thermal reaction time is longer, cause production cost higher, and from its accompanying drawing 4, this positive electrode phase purity is lower, the effect of the capacity of material mainly tri-iron tetroxide during 0.1C when it is coated without carbon.
Therefore, the present invention has carried out improving proposing a kind of method that can obtain stable hexagonal walnut iron lithium silicate aggregation positive electrode on the hydro thermal method basis of prior art, the method substantially reduces the hydro-thermal reaction time, save preparation cost, and the phase purity of gained is higher, capacity without the coated original material of carbon is also higher, is about 120mAh/g during 0.1C.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is the preparation method providing a kind of hexagonal peach-pit shape ferric metasilicate lithium, comprise: by divalence source of iron and silicon dioxide, lithium source hybrid reaction in the solution with surfactant, then obtain ferric metasilicate lithium 150 DEG C ~ 220 DEG C hydro-thermal reactions.Described surfactant is for controlling reaction and crystallization process.
Preferably, described surfactant is alcohols, be particularly preferably the combination of in glycol, diethylene glycol (DEG), tetraethylene glycol, isopropyl alcohol or PEG400 a kind or at least 2 kinds, the typical but non-limiting example of described combination comprises the combination of glycol and diethylene glycol (DEG), the combination of tetraethylene glycol and PEG400, the combination of diethylene glycol (DEG), isopropyl alcohol and PEG400, the combination of glycol, diethylene glycol (DEG), tetraethylene glycol and isopropyl alcohol, the combination etc. of glycol, diethylene glycol (DEG), tetraethylene glycol, isopropyl alcohol and PEG400.
Preferably, the preparation method of described hexagonal peach-pit shape ferric metasilicate lithium comprises the following steps:
(1) in containing the silica dispersions of surfactant, lithium source is added, mixing;
(2) under protective atmosphere, mixed liquor step (1) obtained mixes with divalence source of iron dispersion liquid;
(3) mixed liquor that step (2) obtains is reacted at 150 ~ 220 DEG C;
(4) removal of impurities, obtains hexagonal peach-pit shape ferric metasilicate lithium.
Preferably, step (1) described surfactant is alcohols, be particularly preferably the combination of in glycol, diethylene glycol (DEG), tetraethylene glycol, isopropyl alcohol or PEG400 a kind or at least 2 kinds, the typical but non-limiting example of described combination comprises the combination of glycol and diethylene glycol (DEG), the combination of tetraethylene glycol and PEG400, the combination of diethylene glycol (DEG), isopropyl alcohol and PEG400, the combination of glycol, diethylene glycol (DEG), tetraethylene glycol and isopropyl alcohol, the combination etc. of glycol, diethylene glycol (DEG), tetraethylene glycol, isopropyl alcohol and PEG400.
Preferably, step (1) described silicon dioxide is aerosil.
Preferably, the preparation method of the described silica dispersions containing surfactant of step (1) comprises: ultrasonic disperse preparation aerosil suspension-turbid liquid, then adds surfactant in suspension-turbid liquid.
Preferably, the described lithium source of step (1) is lithium dihydrogen phosphate, lithium carbonate, lithium acetate, lithium formate, lithium citrate, lithium chloride, lithium bromide, lithium hydroxide, tert-butyl alcohol lithium, lithium benzoate, lithium phosphate, phosphoric acid hydrogen two lithium, lithium oxalate, 1 kind in lithium sulfate or the combination of at least 2 kinds, the typical but non-limiting example of described combination has: the combination of lithium carbonate and lithium acetate, the combination of lithium dihydrogen phosphate and lithium bromide, lithium acetate, the combination of lithium formate and lithium citrate, lithium hydroxide, the combination of tert-butyl alcohol lithium and lithium oxalate, lithium hydroxide, tert-butyl alcohol lithium, the combination of lithium benzoate and phosphoric acid hydrogen two lithium, lithium dihydrogen phosphate, lithium citrate, the combination of lithium chloride and lithium bromide, lithium phosphate, phosphoric acid hydrogen two lithium, the combination of lithium oxalate and lithium sulfate, lithium chloride, lithium bromide, lithium hydroxide, the combination of lithium phosphate and phosphoric acid hydrogen two lithium, lithium chloride, lithium bromide, lithium benzoate, the combination etc. of lithium hydroxide and tert-butyl alcohol lithium, be particularly preferably lithium hydroxide.
Preferably, step (1) described mixing temperature is 40 ~ 60 DEG C, more preferably 45 ~ 55 DEG C, particularly preferably 50 DEG C.
Preferably, ultrasonic mixing is mixed into described in step (1).
In raw material of the present invention, the mol ratio of silicon, lithium and iron can by one of ordinary skill in the art according to the product obtained form and material loss in experimentation determines.
Preferably, in the mixed liquor that step (1) obtains, the mol ratio of silicon and lithium is 1:1.5 ~ 1:3, more preferably 1:1.8 ~ 1:2.5, is particularly preferably 1:2.
The described lithium source of step (1) is added in the silica dispersions containing surfactant as far as possible lentamente.
Preferably, in the mixed liquor that step (2) obtains, the mol ratio of silicon and iron is 1:0.6 ~ 1:1.5, more preferably 1:0.8 ~ 1:1.2, is particularly preferably 1:1.
Preferably, the described divalence source of iron of step (2) is ferrous oxalate, ferrous acetate, ferrous sulfate, 1 kind in ferrous phosphate or frerrous chloride or the combination of at least 2 kinds, the typical but non-limiting example of described combination has: the combination of ferrous oxalate and ferrous acetate, the combination of ferrous sulfate and ferrous phosphate, ferrous acetate, the combination of ferrous sulfate and frerrous chloride, ferrous oxalate, ferrous acetate, the combination of ferrous sulfate and frerrous chloride, ferrous oxalate, ferrous acetate, ferrous sulfate, the combination etc. of ferrous phosphate and frerrous chloride, be particularly preferably ferrous sulfate and/or frerrous chloride.
Preferably, step (2) described protective atmosphere is the combination of in helium, neon, argon gas, Krypton, xenon or nitrogen a kind or at least 2 kinds, is particularly preferably argon gas.
Preferably, described mixed liquor step (1) obtained of step (2) mixes with divalence source of iron dispersion liquid and comprises: in the mixed liquor that step (1) obtains, add divalence source of iron dispersion liquid; The intervention of described divalence source of iron dispersion liquid should be tried one's best slowly.
Preferably, step (2) described mixing is under agitation carried out.
Preferably, step (2) described incorporation time is at least 20 minutes, more preferably 25 ~ 40 minutes, is particularly preferably 30 minutes.
Preferably, step (3) described reaction is carried out in autoclave; Preferably, described autoclave has polytetrafluoroethylliner liner.
Preferably, step (3) described reaction temperature is 155 ~ 210 DEG C, is particularly preferably 160 ~ 200 DEG C.
Preferably, step (4) described removal of impurities comprises: washing is also dry; Preferably, described washing is centrifugal supersound washing; Preferably, described drying is carried out in vacuum drying chamber; Preferably, described baking temperature is 40 ~ 120 DEG C, more preferably 60 ~ 110 DEG C, is particularly preferably 100 DEG C; Preferably, described drying time is at least 4 hours, more preferably 5 ~ 10 hours, is particularly preferably 6 ~ 8 hours.
Dispersion liquid of the present invention can be solution also can be suspension-turbid liquid.
The lithium iron silicate material cannot prepared by the method for the invention only has a small amount of dephasign, and crystallinity is good; There is laminated structure in surface; Chemical property is good.
Two of object of the present invention is to provide a kind of hexagonal peach-pit shape ferric metasilicate lithium, it is characterized in that, described hexagonal peach-pit shape ferric metasilicate lithium is prepared by the method for the invention, particle diameter is 0.8-1.2 μm, cross section is hexagonal peach-pit shape, and each hexagonal peach-pit shape aggregation is loosely made up of less nano particle; Described less nano particle refers to the nano particle less than hexagonal peach-pit shape aggregate particle size.
Three of object of the present invention is to provide a kind of lithium ion battery, it is characterized in that, described lithium ion battery comprises hexagonal peach-pit shape ferric metasilicate lithium of the present invention.
Compared with prior art, advantage of the present invention is: lithium iron silicate material cannot prepared by the method for the invention only has a small amount of dephasign, crystallinity is good, granularity is little, without carbon encapsulated material, there is good chemical property, when 0.1C, discharge capacity is about 120mAh/g, and has good cycle characteristics, does not substantially decay through 50 circulation volumes.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates of the product prepared by embodiment 1;
Fig. 2 is the SEM image of the product prepared by embodiment 1;
Fig. 3 is the XRD collection of illustrative plates of the product prepared by embodiment 2;
Fig. 4 is the SEM image of the product prepared by embodiment 2;
Fig. 5 is the XRD collection of illustrative plates of the product prepared by embodiment 3;
Fig. 6 is the SEM image of the product prepared by embodiment 3;
Fig. 7 is the product cycle performance of battery prepared by embodiment 2;
Fig. 8 is the TEM figure of the product prepared by embodiment 1.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
By gas phase SiO 2water bath sonicator dispersion in aqueous, adds 1mL diethylene glycol (DEG) surfactant simultaneously, after being uniformly dispersed, slowly adds the LiOH aqueous solution, and continue water bath sonicator, control temperature is at about 50 DEG C, until solution is become transparent from milky.Solution being transferred to polytetrafluoroethylene is in the reactor of liner, under argon shield, add FeSO 4the aqueous solution, now total amount of liquid is about 25mL, sealing stir 30min, after by reactor constant temperature 8h at 200 DEG C.
By product through distilled water cyclic washing, 100 DEG C of dryings in vacuum drying chamber, obtain hexagonal peach-pit shape ferric metasilicate lithium powder.
Fig. 1 is the XRD collection of illustrative plates of this example product, and the obtained lithium iron silicate material cannot of known embodiment only has a small amount of dephasign, and crystallinity is good.
Fig. 2 is the SEM image of this example product, and material is be about the hexagonal peach-pit shape ferric metasilicate lithium of 1 μm uniformly, and scheme its surface known by the TEM of Fig. 8 and there is laminated structure, known by energy dispersion X-ray spectrum, this structure is ferric metasilicate lithium.
For test chemical property, lithium iron silicate material cannot obtained above is made battery, its concrete steps are as follows: the black and binding agent PVDF(Kynoar with conductive acetylene respectively by the material of gained) according to mass ratio 75:15:10 mixed grinding, use NMP(N methyl pyrrolidone) this mixture is modulated into slurry, all be coated on aluminium foil, 110 DEG C of vacuumize 12h, dicing after taking out, is pressed into battery anode slice under 20MPa.With lithium sheet for negative pole, the LiPF6(lithium hexafluoro phosphate of 1mol/L) EC(ethyl carbonate ester), DMC(dimethyl carbonate) solution (volume ratio is 1:1) is electrolyte, take polyethylene film as barrier film, in the glove box being full of argon gas, be assembled into button cell.
Use battery testing cabinet, setting voltage scope is 1.5-4.8V, by permanent direct current charge-discharge, it is a circulation that battery completes a discharge and recharge, as shown in the curve 1 in Fig. 7, be 107.6mAh/g in the discharge capacity first of 0.1C, after 4 circulations, reach maximum 117.4mAh/g, the capacity after 50 times that circulates is 109.3mAh/g, and cycle performance is good.
Embodiment 2
By gas phase SiO 2water bath sonicator dispersion in aqueous, adds 1mL isopropyl alcohol surfactant simultaneously, after being uniformly dispersed, slowly adds the LiOH aqueous solution, and continue water bath sonicator, control temperature is at about 50 DEG C, until solution is become transparent from milky.Solution being transferred to polytetrafluoroethylene is in the reactor of liner, under argon shield, add FeSO 4the aqueous solution, now total amount of liquid is about 25mL, sealing stir 30min, after by reactor constant temperature 8h at 200 DEG C.
By product through distilled water cyclic washing, 100 DEG C of dryings in vacuum drying chamber, obtain hexagonal peach-pit shape ferric metasilicate lithium powder.
Fig. 3 is the XRD collection of illustrative plates of this example product, and the obtained lithium iron silicate material cannot of known embodiment only has a small amount of dephasign, and crystallinity is good.
Fig. 4 is the SEM image of this example product, and material is be about the hexagonal peach-pit shape ferric metasilicate lithium of 1 μm uniformly.
The lithium iron silicate material cannot obtained by the present embodiment according to the method for embodiment 1 makes battery, the circulation volume performance of test battery, as shown in the curve 2 in Fig. 7, be 82.2mAh/g in the discharge capacity first of 0.1C, maximum 97.8mAh/g is reached after 8 circulations, the capacity after 50 times that circulates is 85.9mAh/g, and cycle performance is good.
Embodiment 3
By gas phase SiO 2water bath sonicator dispersion in aqueous, adds 3mL diethylene glycol (DEG) surfactant simultaneously, after being uniformly dispersed, slowly adds the LiOH aqueous solution, and continue water bath sonicator, control temperature is at about 50 DEG C, until solution is become transparent from milky.Solution being transferred to polytetrafluoroethylene is in the reactor of liner, under argon shield, add FeSO 4the aqueous solution, now total amount of liquid is about 25mL, sealing stir 30min, after by reactor constant temperature 8h at 200 DEG C.
By product through distilled water cyclic washing, 100 DEG C of dryings in vacuum drying chamber, obtain hexagonal peach-pit shape ferric metasilicate lithium powder.
Fig. 5 is the XRD collection of illustrative plates of this example product, and the obtained lithium iron silicate material cannot of known embodiment only has a small amount of dephasign, and crystallinity is good.
Fig. 6 is the SEM image of this example product, and material is be about the hexagonal peach-pit shape ferric metasilicate lithium of 1 μm uniformly.
The lithium iron silicate material cannot obtained by the present embodiment according to the method for embodiment 1 makes battery, the circulation volume performance of test battery, as shown in the curve 3 in Fig. 7, be 85.7mAh/g in the discharge capacity first of 0.1C, maximum 97.6mAh/g is reached after 4 circulations, the capacity after 50 times that circulates is 83.0mAh/g, and cycle performance is good.
Embodiment 4
By gas phase SiO 2water bath sonicator dispersion in aqueous, adds 5mL PEG400 surfactant simultaneously, after being uniformly dispersed, slowly adds the lithium citrate aqueous solution, and continue water bath sonicator, control temperature is at about 40 DEG C, until solution is become transparent from milky.Solution being transferred to polytetrafluoroethylene is in the reactor of liner, and under argon shield, add the aqueous suspension of ferrous oxalate, now total amount of liquid is about 25mL, sealing stir 20min, after by reactor constant temperature 15h at 150 DEG C.
By product through distilled water cyclic washing, 40 DEG C of dryings in vacuum drying chamber, obtain hexagonal peach-pit shape ferric metasilicate lithium powder.
The lithium iron silicate material cannot obtained by the present embodiment according to the method for embodiment 1 makes battery, the circulation volume performance of test battery, be 105.7mAh/g in the discharge capacity first of 0.1C, maximum 117.6mAh/g is reached after 4 circulations, the capacity after 50 times that circulates is 108.0mAh/g, and cycle performance is good.
Embodiment 5
By gas phase SiO 2water bath sonicator dispersion in aqueous, adds 2mL glycol surfactant simultaneously, after being uniformly dispersed, slowly adds the lithium acetate aqueous solution, and continue water bath sonicator, control temperature is at about 60 DEG C, until solution is become transparent from milky.Solution being transferred to polytetrafluoroethylene is in the reactor of liner, and under argon shield, add the aqueous suspension of ferrous oxalate, now total amount of liquid is about 25mL, sealing stir 40min, after by reactor constant temperature 6h at 220 DEG C.
By product through distilled water cyclic washing, 120 DEG C of dryings in vacuum drying chamber, obtain hexagonal peach-pit shape ferric metasilicate lithium powder.
The lithium iron silicate material cannot obtained by the present embodiment according to the method for embodiment 1 makes battery, the circulation volume performance of test battery is 98.2mAh/g in the discharge capacity first of 0.1C, reaches maximum 102.6mAh/g after 4 circulations, the capacity after 50 times that circulates is 99.0mAh/g, and cycle performance is good.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.

Claims (26)

1. a preparation method for hexagonal peach-pit shape ferric metasilicate lithium, is characterized in that, said method comprising the steps of:
(1) in containing the silica dispersions of surfactant, lithium source is added, mixing; In the mixed liquor obtained, the mol ratio of silicon and lithium is 1:1.5 ~ 1:3;
(2) under protective atmosphere, mixed liquor step (1) obtained mixes with divalence source of iron dispersion liquid; In the mixed liquor obtained, the mol ratio of silicon and iron is 1:0.6 ~ 1:1.5;
(3) mixed liquor that step (2) obtains is reacted at 150 ~ 220 DEG C;
(4) removal of impurities, obtains hexagonal peach-pit shape ferric metasilicate lithium.
2. the method for claim 1, is characterized in that, step (1) described surfactant is the combination of in diethylene glycol (DEG), tetraethylene glycol, isopropyl alcohol or PEG400 a kind or at least 2 kinds.
3. the method for claim 1, is characterized in that, step (1) described silicon dioxide is aerosil.
4. the method for claim 1, it is characterized in that, the preparation method of the described silica dispersions containing surfactant of step (1) comprises: ultrasonic disperse preparation aerosil suspension-turbid liquid, then adds surfactant in suspension-turbid liquid.
5. the method for claim 1, it is characterized in that, the described lithium source of step (1) is the combination of in lithium dihydrogen phosphate, lithium carbonate, lithium acetate, lithium formate, lithium citrate, lithium chloride, lithium bromide, lithium hydroxide, tert-butyl alcohol lithium, lithium benzoate, lithium phosphate, phosphoric acid hydrogen two lithium, lithium oxalate, lithium sulfate a kind or at least 2 kinds.
6. method as claimed in claim 5, it is characterized in that, described lithium source is lithium hydroxide.
7. the method for claim 1, is characterized in that, step (1) described mixing temperature is 40 ~ 60 DEG C.
8. method as claimed in claim 7, it is characterized in that, described mixing temperature is 45 ~ 55 DEG C.
9. the method for claim 1, is characterized in that, step is mixed into ultrasonic mixing described in (1).
10. the method for claim 1, is characterized in that, in the mixed liquor that step (1) obtains, the mol ratio of silicon and lithium is 1:1.8 ~ 1:2.5.
11. the method for claim 1, is characterized in that, in the mixed liquor that step (2) obtains, the mol ratio of silicon and iron is 1:0.8 ~ 1:1.2.
12. the method for claim 1, is characterized in that, the described divalence source of iron of step (2) is the combination of in ferrous oxalate, ferrous acetate, ferrous sulfate, ferrous phosphate or frerrous chloride a kind or at least 2 kinds.
13. methods as claimed in claim 12, it is characterized in that, described divalence source of iron is ferrous sulfate and/or frerrous chloride.
14. the method for claim 1, is characterized in that, step (2) described protective atmosphere is the combination of in helium, neon, argon gas, Krypton, xenon or nitrogen a kind or at least 2 kinds.
15. methods as claimed in claim 14, it is characterized in that, described protective atmosphere is argon gas.
16. the method for claim 1, it is characterized in that, described mixed liquor step (1) obtained of step (2) mixes with divalence source of iron dispersion liquid and comprises: in the mixed liquor that step (1) obtains, add divalence source of iron dispersion liquid.
17. the method for claim 1, is characterized in that, step (2) described mixing is under agitation carried out.
18. the method for claim 1, is characterized in that, step (2) described incorporation time is at least 20 minutes.
19. methods as claimed in claim 18, it is characterized in that, described incorporation time is 25 ~ 40 minutes.
20. the method for claim 1, is characterized in that, step (3) described reaction is carried out in autoclave.
21. methods as claimed in claim 20, it is characterized in that, described autoclave has polytetrafluoroethylliner liner.
22. the method for claim 1, is characterized in that, step (3) described reaction temperature is 155 ~ 210 DEG C.
23. methods as claimed in claim 22, it is characterized in that, described reaction temperature is 160 ~ 200 DEG C.
24. the method for claim 1, is characterized in that, step (4) described removal of impurities comprises: washing is also dry; Described washing is centrifugal supersound washing; Described drying is carried out in vacuum drying chamber; Described baking temperature is 40 ~ 120 DEG C; Described drying time is at least 4 hours.
25. 1 kinds of hexagonal peach-pit shape ferric metasilicate lithiums, it is characterized in that, described hexagonal peach-pit shape ferric metasilicate lithium is prepared by method described in any one of claim 1-24, and particle diameter is 0.8-1.2 μm, cross section is hexagonal peach-pit shape, and each hexagonal peach-pit shape aggregation is made up of nano particle.
26. 1 kinds of lithium ion batteries, is characterized in that, described lithium ion battery comprises hexagonal peach-pit shape ferric metasilicate lithium described in claim 25.
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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104009224A (en) * 2014-05-13 2014-08-27 昆明理工大学 Method for synthesizing lithium iron silicate positive electrode material by using chrysotile asbestos as raw material
CN105406037B (en) * 2015-11-02 2018-01-02 国家纳米科学中心 A kind of porous ferric metasilicate lithium, preparation method and its usage
CN106410195A (en) * 2016-12-01 2017-02-15 河北大学 Preparation method of carbon-free lithium ferrous silicate lithium ion battery cathode material
CN112018338B (en) * 2019-05-31 2021-07-09 台南大学 Method for preparing silicon-based electrode material, silicon-based electrode material and lithium ion battery
CN113948698A (en) * 2021-10-14 2022-01-18 浙江长兴中俄新能源材料技术研究院有限公司 Preparation method of nano polyanionic material carbon composite lithium iron silicate

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Hierarchical shuttle-like Li2FeSiO4 as a highly efficient cathode material for lithium-ion batteries.;Jinlong Yang et al.;《Journal of Power Sources》;20130528;第242卷;第172页第1竖栏至第173页第1竖栏 *
表面活性剂对Li2FeSiO4储锂性能的影响;杭立峰 等.;《电池工业》;20121031;第17卷(第5期);全文 *

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