CN103400981A - Hexagonal walnut iron lithium silicate aggregation and preparation method thereof - Google Patents
Hexagonal walnut iron lithium silicate aggregation and preparation method thereof Download PDFInfo
- Publication number
- CN103400981A CN103400981A CN2013102771841A CN201310277184A CN103400981A CN 103400981 A CN103400981 A CN 103400981A CN 2013102771841 A CN2013102771841 A CN 2013102771841A CN 201310277184 A CN201310277184 A CN 201310277184A CN 103400981 A CN103400981 A CN 103400981A
- Authority
- CN
- China
- Prior art keywords
- lithium
- hexagonal
- particularly preferably
- peach
- surfactant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a method for preparing a hexagonal walnut iron lithium silicate aggregation cathode material by a hydrothermal method, wherein a preparation process comprises: firstly mixing and reacting a ferrous salt, a silica dispersion liquid and a lithium hydroxide solution in a certain proportion under existence of a surfactant, and finally obtaining single-phase iron lithium silicate by hydrothermal reaction under a proper condition. The iron lithium silicate aggregation prepared by the method has about 1mum of average particle size, the cross section shows a hexagonal walnut shape, and each hexagonal walnut-shaped aggregation is loosely composed of smaller nano particles.
Description
Technical field
The present invention relates to the energy and material preparing technical field, particularly, the present invention relates to a kind of hexagonal peach-pit shape ferric metasilicate lithium aggregation and preparation method thereof.
Background technology
Along with developing rapidly of various mobile electronic devices, 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 the keys of its development of restriction.Since reported first LiFePO4 in 1997 can be used as anode material for lithium-ion batteries, LiFePO4 was 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 the high performance lithium ion battery anode material with better conductivity is found in expectation.And silicate lithium intercalation compound (Li
2MSiO
4, M=Fe, Mn, Co, Ni) and due to the existence of its unique Si-O key, its electron conduction likely is better than the previous LiFePO4 of finding, and theoretical specific capacity is close with LiFePO4 when the single electron removal lithium embedded.Therefore, be subject to people's extensive concern.At present, research work mainly still concentrates on the exploration of material synthesis method.What is more important, compare with LiFePO4, and when ferric metasilicate lithium took off 2 lithium ions of embedding, its theoretical specific capacity was about the twice of LiFePO4.Therefore, the synthetic of research ferric metasilicate lithium has important science and a practical significance.
At present, the typical preparation method 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. the people by high temperature solid-state method take lithium metasilicate, ferrous oxalate and tetraethoxysilane as raw material, after mixing at CO/CO
2The lower 750 ℃ of reaction 24h high temperature of atmosphere have synthesized Li
2FeSiO
4/ C composite material.Hydro thermal method: R.Dominko(R.Dominko etc., Electrochemistry Communications8 (2006) 217-222) etc. the people with silicon dioxide through the ultrasonic auxiliary lithium hydroxide solution that is dispersed in, then mix with solution of ferrous chloride, in the enclosed high pressure still more than 150 ℃ of isothermal reaction 72h, the powder that obtains is used the distilled water cyclic washing under Ar atmosphere, obtain the ferric metasilicate lithium powder after drying.Sol-gal process: R.Dominko(R.Dominko, Journal of Power Sources184 (2008) 462-468) etc. appearance is raw material with the mixture of ironic citrate, ferric nitrate, lithium acetate and SiO 2 powder, prepare gel in ultrasonic water bath, drying, react 1h and obtain ferric metasilicate lithium under the inert atmosphere of 700 ℃ after grinding.
In said method, material grains and particle that high temperature solid phase synthesis obtains are large, 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, is difficult to obtain single-phase ferric metasilicate lithium.
In addition, CN103078120A discloses a kind of preparation method with ferrosilicon silicate of lithium anode material for lithium-ion batteries of hierarchical organization, comprise the following steps: 1) add molysite and organic acid or organic amine in the mixed solvent of Organic Alcohol and distilled water, stirring and being made into iron concentration is 0.0001～3M solution, Organic Alcohol and distilled water volume proportion are 40:20～0:60, and be stand-by; 2) silicon source material and lithium salts are dispersed in distilled water, stirred 10～60 minutes, being made into silicon and lithium concentration is respectively that 0.0001～3M mixed liquor is stand-by; 3) with mixed solution and the step 2 of step 1)) 10-60 minute reactor of packing into of mixed solution mix and blend, lithium in the reactant of its mixing: iron: silicon mol ratio=2:1:1～5:1:1; 4) reactor of step 3) is put into the hydro-thermal reaction case and reacted 4-8 days under 180-210 ℃ of hydrothermal condition, products therefrom washs and the dry ferrosilicon silicate of lithium that obtains hierarchical organization, but the method hydro-thermal reaction time is longer, cause production cost higher, and by its accompanying drawing 4 as can be known, this positive electrode phase purity is lower, when it coats without carbon during 0.1C the capacity of material be mainly the effect of tri-iron tetroxide.
Therefore, the present invention has carried out improving a kind of method that can obtain to stablize hexagonal peach-pit shape ferric metasilicate lithium aggregation positive electrode that proposed on the hydro thermal method basis of prior art, the method has shortened the hydro-thermal reaction time greatly, saved preparation cost, and the phase purity of gained is higher, the capacity that coats original material without carbon is also higher, is about 120mAh/g during 0.1C.
Summary of the invention
For the deficiencies in the prior art, one of purpose of the present invention is to provide a kind of preparation method of hexagonal peach-pit shape ferric metasilicate lithium, comprise:, with divalence source of iron and silicon dioxide, lithium source hybrid reaction in having the solution of surfactant, then 150 ℃～220 ℃ hydro-thermal reactions, obtain ferric metasilicate lithium.Described surfactant is used for controlling reaction and crystallization process.
Preferably, described surfactant is alcohols, be particularly preferably a kind or the combination of at least 2 kinds in glycol, diethylene glycol (DEG), tetraethylene glycol, isopropyl alcohol or PEG400, 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 of glycol, diethylene glycol (DEG), tetraethylene glycol, isopropyl alcohol and PEG400 etc.
Preferably, the preparation method of described hexagonal peach-pit shape ferric metasilicate lithium comprises the following steps:
(1) add the lithium source in containing the silica dispersions of surfactant, mix;
(2) under protective atmosphere, the mixed liquor that step (1) is obtained mixes with divalence source of iron dispersion liquid;
(3) mixed liquor that step (2) is obtained reacts at 150～220 ℃;
(4) removal of impurities, obtain hexagonal peach-pit shape ferric metasilicate lithium.
Preferably, the described surfactant of step (1) is alcohols, be particularly preferably a kind or the combination of at least 2 kinds in glycol, diethylene glycol (DEG), tetraethylene glycol, isopropyl alcohol or PEG400, 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 of glycol, diethylene glycol (DEG), tetraethylene glycol, isopropyl alcohol and PEG400 etc.
Preferably, the described silicon dioxide of step (1) is aerosil.
Preferably, step (1) is the described preparation method who contains the silica dispersions of surfactant comprise: then ultrasonic dispersion preparation aerosil suspension-turbid liquid adds surfactant in suspension-turbid liquid.
preferably, the described lithium of step (1) source 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 lithiums, lithium oxalate, 1 kind or the combination of at least 2 kinds in lithium sulfate, 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 lithiums, lithium dihydrogen phosphate, lithium citrate, the combination of lithium chloride and lithium bromide, lithium phosphate, phosphoric acid hydrogen two lithiums, the combination of lithium oxalate and lithium sulfate, lithium chloride, lithium bromide, lithium hydroxide, the combination of lithium phosphate and phosphoric acid hydrogen two lithiums, lithium chloride, lithium bromide, lithium benzoate, the combination of lithium hydroxide and tert-butyl alcohol lithium etc., be particularly preferably lithium hydroxide.
Preferably, the described mixing temperature of step (1) is 40～60 ℃, more preferably 45～55 ℃, and particularly preferably 50 ℃.
Preferably, step (1) is described is mixed into ultrasonic mixing.
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 that obtains form and experimentation in material loss determine.
Preferably, in the resulting mixed liquor of step (1), the mol ratio of silicon and lithium is 1:1.5～1:3, and more preferably 1:1.8～1:2.5, be particularly preferably 1:2.
The described lithium of step (1) source is added in the silica dispersions that contains surfactant as far as possible lentamente.
Preferably, in the resulting mixed liquor of step (2), the mol ratio of silicon and iron is 1:0.6～1:1.5, and more preferably 1:0.8～1:1.2, be particularly preferably 1:1.
preferably, the described divalence source of iron of step (2) is ferrous oxalate, ferrous acetate, ferrous sulfate, 1 kind or the combination of at least 2 kinds in ferrous phosphate or frerrous chloride, 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 of ferrous phosphate and frerrous chloride etc., be particularly preferably ferrous sulfate and/or frerrous chloride.
Preferably, the described protective atmosphere of step (2) is a kind or the combination of at least 2 kinds in helium, neon, argon gas, Krypton, xenon or nitrogen, is particularly preferably argon gas.
Preferably, the described mixed liquor that step (1) is obtained of step (2) mixes and comprises with divalence source of iron dispersion liquid: add divalence source of iron dispersion liquid in the mixed liquor that step (1) obtains; The intervention of described divalence source of iron dispersion liquid should be tried one's best slowly.
Preferably, the described mixing of step (2) is under agitation carried out.
Preferably, the described incorporation time of step (2) is at least 20 minutes, more preferably 25～40 minutes, is particularly preferably 30 minutes.
Preferably, the described reaction of step (3) is carried out in autoclave; Preferably, described autoclave has polytetrafluoroethylliner liner.
Preferably, the described reaction temperature of step (3) is 155～210 ℃, is particularly preferably 160～200 ℃.
Preferably, the described removal of impurities of step (4) 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 ℃, more preferably 60～110 ℃, is particularly preferably 100 ℃; Preferably, be at least 4 hours described drying time, more preferably 5～10 hours, is particularly preferably 6～8 hours.
Dispersion liquid of the present invention can also can be suspension-turbid liquid for solution.
The ferric metasilicate lithium material for preparing 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 purpose 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 μ m, cross section is hexagonal peach-pit shape, and each hexagonal peach-pit shape aggregation is comprised of than loosely less nano particle; Described less nano particle refers to than the little nano particle of hexagonal peach-pit shape aggregate particle size.
Three of purpose 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: the ferric metasilicate lithium material of the method for the invention preparation only has a small amount of dephasign, crystallinity is good, granularity is little, has good chemical property without carbon encapsulated material, discharge capacity is about 120mAh/g when 0.1C, and has good cycle characteristics, through 50 circulation volumes, substantially there is no decay.
Description of drawings
Fig. 1 is the XRD collection of illustrative plates of the prepared product of embodiment 1;
Fig. 2 is the SEM image of the prepared product of embodiment 1;
Fig. 3 is the XRD collection of illustrative plates of the prepared product of embodiment 2;
Fig. 4 is the SEM image of the prepared product of embodiment 2;
Fig. 5 is the XRD collection of illustrative plates of the prepared product of embodiment 3;
Fig. 6 is the SEM image of the prepared product of embodiment 3;
Fig. 7 is the prepared product cycle performance of battery of embodiment 2;
Fig. 8 is the TEM figure of the prepared product of 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 helps to understand the present invention, should not be considered as concrete restriction of the present invention.
With gas phase SiO
2The ultrasonic dispersion of water-bath in the aqueous solution, add 1mL diethylene glycol (DEG) surfactant simultaneously, after being uniformly dispersed, slowly adds the LiOH aqueous solution, continues water-bath ultrasonic, controls temperature 50 ℃ of left and right, until that solution is become by milky is transparent.Solution is transferred in the reactor that polytetrafluoroethylene is liner, adds FeSO under argon shield
4The aqueous solution, this moment, total amount of liquid was about 25mL, 30min is stirred in sealing, after with reactor at 200 ℃ of lower constant temperature 8h.
Through the distilled water cyclic washing, 100 ℃ of dryings in vacuum drying chamber, obtain hexagonal peach-pit shape ferric metasilicate lithium powder with product.
Fig. 1 is the XRD collection of illustrative plates of this example product, and the ferric metasilicate lithium material that makes of this embodiment only has a small amount of dephasign as can be known, and crystallinity is good.
Fig. 2 is the SEM image of this example product, and material is for being about uniformly the hexagonal peach-pit shape ferric metasilicate lithium of 1 μ m, by the TEM figure of Fig. 8, has laminated structure in its surface as can be known, by energy dispersion X ray spectrum, is known, this structure is ferric metasilicate lithium.
For the test chemical property, ferric metasilicate lithium material obtained above is made battery, its concrete steps are as follows: the material of gained is deceived and binding agent PVDF(Kynoar with conductive acetylene respectively) according to mass ratio 75:15:10 mixed grinding, use the NMP(N methyl pyrrolidone) this mixture is modulated into slurry, all be coated on aluminium foil, 110 ℃ of vacuumize 12h, dicing after taking out, be pressed into battery anode slice under 20MPa.Take the lithium sheet as 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, be assembled into button cell in being full of the glove box of argon gas.
Use the battery testing cabinet, the setting voltage scope is 1.5-4.8V, discharge and recharge by permanent direct current, battery is completed and once discharged and recharged is a circulation, as shown in the curve 1 in Fig. 7, be 107.6mAh/g in the discharge capacity first of 0.1C, reach maximum 117.4mAh/g after 4 circulations, the capacity after 50 times that circulates is 109.3mAh/g, and cycle performance is good.
Embodiment 2
With gas phase SiO
2The ultrasonic dispersion of water-bath in the aqueous solution, add 1mL isopropyl alcohol surfactant simultaneously, after being uniformly dispersed, slowly adds the LiOH aqueous solution, continues water-bath ultrasonic, controls temperature 50 ℃ of left and right, until that solution is become by milky is transparent.Solution is transferred in the reactor that polytetrafluoroethylene is liner, adds FeSO under argon shield
4The aqueous solution, this moment, total amount of liquid was about 25mL, 30min is stirred in sealing, after with reactor at 200 ℃ of lower constant temperature 8h.
Through the distilled water cyclic washing, 100 ℃ of dryings in vacuum drying chamber, obtain hexagonal peach-pit shape ferric metasilicate lithium powder with product.
Fig. 3 is the XRD collection of illustrative plates of this example product, and the ferric metasilicate lithium material that makes of this embodiment only has a small amount of dephasign as can be known, and crystallinity is good.
Fig. 4 is the SEM image of this example product, and material is for being about uniformly the hexagonal peach-pit shape ferric metasilicate lithium of 1 μ m.
Method according to embodiment 1 is made battery with the ferric metasilicate lithium material that the present embodiment obtains, the circulation volume performance of test battery, as shown in the curve 2 in Fig. 7, discharge capacity first at 0.1C is 82.2mAh/g, reach maximum 97.8mAh/g after 8 circulations, the capacity after 50 times that circulates is 85.9mAh/g, and cycle performance is good.
With gas phase SiO
2The ultrasonic dispersion of water-bath in the aqueous solution, add 3mL diethylene glycol (DEG) surfactant simultaneously, after being uniformly dispersed, slowly adds the LiOH aqueous solution, continues water-bath ultrasonic, controls temperature 50 ℃ of left and right, until that solution is become by milky is transparent.Solution is transferred in the reactor that polytetrafluoroethylene is liner, adds FeSO under argon shield
4The aqueous solution, this moment, total amount of liquid was about 25mL, 30min is stirred in sealing, after with reactor at 200 ℃ of lower constant temperature 8h.
Through the distilled water cyclic washing, 100 ℃ of dryings in vacuum drying chamber, obtain hexagonal peach-pit shape ferric metasilicate lithium powder with product.
Fig. 5 is the XRD collection of illustrative plates of this example product, and the ferric metasilicate lithium material that makes of this embodiment only has a small amount of dephasign as can be known, and crystallinity is good.
Fig. 6 is the SEM image of this example product, and material is for being about uniformly the hexagonal peach-pit shape ferric metasilicate lithium of 1 μ m.
Method according to embodiment 1 is made battery with the ferric metasilicate lithium material that the present embodiment obtains, the circulation volume performance of test battery, as shown in the curve 3 in Fig. 7, discharge capacity first at 0.1C is 85.7mAh/g, reach maximum 97.6mAh/g after 4 circulations, the capacity after 50 times that circulates is 83.0mAh/g, and cycle performance is good.
Embodiment 4
With gas phase SiO
2The ultrasonic dispersion of water-bath in the aqueous solution, add 5mL PEG400 surfactant simultaneously, after being uniformly dispersed, slowly adds the lithium citrate aqueous solution, continues water-bath ultrasonic, controls temperature 40 ℃ of left and right, until that solution is become by milky is transparent.Solution is transferred in the reactor that polytetrafluoroethylene is liner, adds the aqueous suspension of ferrous oxalate under argon shield, this moment, total amount of liquid was about 25mL, and 20min is stirred in sealing, after with reactor at 150 ℃ of lower constant temperature 15h.
Through the distilled water cyclic washing, 40 ℃ of dryings in vacuum drying chamber, obtain hexagonal peach-pit shape ferric metasilicate lithium powder with product.
Method according to embodiment 1 is made battery with the ferric metasilicate lithium material that the present embodiment obtains, the circulation volume performance of test battery, discharge capacity first at 0.1C is 105.7mAh/g, reach maximum 117.6mAh/g after 4 circulations, the capacity after 50 times that circulates is 108.0mAh/g, and cycle performance is good.
With gas phase SiO
2The ultrasonic dispersion of water-bath in the aqueous solution, add 2mL glycol surfactant simultaneously, after being uniformly dispersed, slowly adds the lithium acetate aqueous solution, continues water-bath ultrasonic, controls temperature 60 ℃ of left and right, until that solution is become by milky is transparent.Solution is transferred in the reactor that polytetrafluoroethylene is liner, adds the aqueous suspension of ferrous oxalate under argon shield, this moment, total amount of liquid was about 25mL, and 40min is stirred in sealing, after with reactor at 220 ℃ of lower constant temperature 6h.
Through the distilled water cyclic washing, 120 ℃ of dryings in vacuum drying chamber, obtain hexagonal peach-pit shape ferric metasilicate lithium powder with product.
Method according to embodiment 1 is made battery with the ferric metasilicate lithium material that the present embodiment obtains, the circulation volume performance of test battery, be 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's statement, 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, does not mean that namely the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. the preparation method of a hexagonal peach-pit shape ferric metasilicate lithium comprises:, with divalence source of iron and silicon dioxide, lithium source hybrid reaction in having the solution of surfactant, then 150 ℃～220 ℃ hydro-thermal reactions, obtain ferric metasilicate lithium.
2. the method for claim 1, is characterized in that, described surfactant is alcohols, is particularly preferably a kind or the combination of at least 2 kinds in glycol, diethylene glycol (DEG), tetraethylene glycol, isopropyl alcohol or PEG400.
3. method as claimed in claim 1 or 2, is characterized in that, said method comprising the steps of:
(1) add the lithium source in containing the silica dispersions of surfactant, mix;
(2) under protective atmosphere, the mixed liquor that step (1) is obtained mixes with divalence source of iron dispersion liquid;
(3) mixed liquor that step (2) is obtained reacts at 150～220 ℃;
(4) removal of impurities, obtain hexagonal peach-pit shape ferric metasilicate lithium.
4. method as claimed in claim 3, is characterized in that, the described surfactant of step (1) is alcohols, is particularly preferably a kind or the combination of at least 2 kinds in glycol, diethylene glycol (DEG), tetraethylene glycol, isopropyl alcohol or PEG400;
Preferably, the described silicon dioxide of step (1) is aerosil;
Preferably, step (1) is the described preparation method who contains the silica dispersions of surfactant comprise: then ultrasonic dispersion preparation aerosil suspension-turbid liquid adds surfactant in suspension-turbid liquid.
5. method as described in claim 3 or 4, it is characterized in that, the described lithium of step (1) source is a kind or the combination of at least 2 kinds 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 lithiums, lithium oxalate, lithium sulfate, is particularly preferably lithium hydroxide;
Preferably, the described mixing temperature of step (1) is 40～60 ℃, more preferably 45～55 ℃, and particularly preferably 50 ℃;
Preferably, step (1) is described is mixed into ultrasonic mixing;
Preferably, in the resulting mixed liquor of step (1), the mol ratio of silicon and lithium is 1:1.5～1:3, and more preferably 1:1.8～1:2.5, be particularly preferably 1:2.
6., as the described method of claim 3-5 any one, it is characterized in that, in the resulting mixed liquor of step (2), the mol ratio of silicon and iron is 1:0.6～1:1.5, and more preferably 1:0.8～1:1.2, be particularly preferably 1:1;
Preferably, the described divalence source of iron of step (2) is a kind or the combination of at least 2 kinds in ferrous oxalate, ferrous acetate, ferrous sulfate, ferrous phosphate or frerrous chloride, is particularly preferably ferrous sulfate and/or frerrous chloride;
Preferably, the described protective atmosphere of step (2) is a kind or the combination of at least 2 kinds in helium, neon, argon gas, Krypton, xenon or nitrogen, is particularly preferably argon gas.
7., as the described method of claim 3-6 any one, it is characterized in that, the described mixed liquor that step (1) is obtained of step (2) mixes and comprises with divalence source of iron dispersion liquid: add divalence source of iron dispersion liquid in the mixed liquor that step (1) obtains;
Preferably, the described mixing of step (2) is under agitation carried out;
Preferably, the described incorporation time of step (2) is at least 20 minutes, more preferably 25～40 minutes, is particularly preferably 30 minutes.
8., as the described method of claim 3-7 any one, it is characterized in that, the described reaction of step (3) is carried out in autoclave; Preferably, described autoclave has polytetrafluoroethylliner liner;
Preferably, the described reaction temperature of step (3) is 155～210 ℃, is particularly preferably 160～200 ℃;
Preferably, the described removal of impurities of step (4) 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 ℃, more preferably 60～110 ℃, is particularly preferably 100 ℃; Preferably, be at least 4 hours described drying time, more preferably 5～10 hours, is particularly preferably 6～8 hours.
9. hexagonal peach-pit shape ferric metasilicate lithium, it is characterized in that, described hexagonal peach-pit shape ferric metasilicate lithium is by the described method preparation of claim 1-8 any one, and particle diameter is 0.8-1.2 μ m, cross section is hexagonal peach-pit shape, and each hexagonal peach-pit shape aggregation is comprised of nano particle.
10. a lithium ion battery, is characterized in that, described lithium ion battery comprises the described hexagonal peach-pit of claim 9 shape ferric metasilicate lithium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310277184.1A CN103400981B (en) | 2013-07-03 | 2013-07-03 | A kind of hexagonal walnut iron lithium silicate aggregation and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310277184.1A CN103400981B (en) | 2013-07-03 | 2013-07-03 | A kind of hexagonal walnut iron lithium silicate aggregation and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103400981A true CN103400981A (en) | 2013-11-20 |
| CN103400981B CN103400981B (en) | 2015-10-21 |
Family
ID=49564562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310277184.1A Active CN103400981B (en) | 2013-07-03 | 2013-07-03 | A kind of hexagonal walnut iron lithium silicate aggregation and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103400981B (en) |
Cited By (5)
| 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 |
| CN105406037A (en) * | 2015-11-02 | 2016-03-16 | 国家纳米科学中心 | Porous lithium iron silicate and preparation method and application thereof |
| 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 |
| CN112018338A (en) * | 2019-05-31 | 2020-12-01 | 张家钦 | 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 |
-
2013
- 2013-07-03 CN CN201310277184.1A patent/CN103400981B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| JINLONG YANG ET AL.: "Hierarchical shuttle-like Li2FeSiO4 as a highly efficient cathode material for lithium-ion batteries.", 《JOURNAL OF POWER SOURCES》, vol. 242, 28 May 2013 (2013-05-28) * |
| 杭立峰 等.: "表面活性剂对Li2FeSiO4储锂性能的影响", 《电池工业》, vol. 17, no. 5, 31 October 2012 (2012-10-31) * |
Cited By (6)
| 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 |
| CN105406037A (en) * | 2015-11-02 | 2016-03-16 | 国家纳米科学中心 | Porous lithium iron silicate and preparation method and application thereof |
| 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 |
| CN112018338A (en) * | 2019-05-31 | 2020-12-01 | 张家钦 | Method for preparing silicon-based electrode material, silicon-based electrode material and lithium ion battery |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103400981B (en) | 2015-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104795560B (en) | A kind of rich sodium P2 phase layered oxide materials and its production and use | |
| CN101955175B (en) | Industrial preparation method for lithium iron phosphate | |
| CN103972497B (en) | Lithium ion battery Co2snO4/ C nano composite negative pole material and preparation and application thereof | |
| CN101630733B (en) | LiFePO4/C preparation method | |
| CN102104144B (en) | Method for preparing lithium iron phosphate compound anode material | |
| CN105470455A (en) | Modified lithium ion battery positive electrode material and preparation method therefor | |
| CN103400981B (en) | A kind of hexagonal walnut iron lithium silicate aggregation and preparation method thereof | |
| CN103137950B (en) | A kind of height ratio capacity lithium ion battery cathode material and its preparation method | |
| CN107768636A (en) | A kind of preparation method of high power capacity fluoride/porous carbon composite anode material | |
| CN101807690B (en) | Preparation method of lithium ion battery ferric metasilicate lithium positive electrode material | |
| CN102838102B (en) | Preparation method of lithium iron phosphate monocrystalline nanorods | |
| CN106935830B (en) | lithium ion battery composite positive electrode material and preparation method and application thereof | |
| CN105406037A (en) | Porous lithium iron silicate and preparation method and application thereof | |
| CN105226267A (en) | Three dimensional carbon nanotubes modifies spinel nickel lithium manganate material and its preparation method and application | |
| CN104810513B (en) | A kind of lithium ion battery negative material and preparation method thereof | |
| CN104868110A (en) | Graphene-oriented mesoporous Co2V2O7 nanosheet material and production method and application thereof | |
| CN109244458A (en) | Three-dimensional netted porous graphene/iron phosphate compound anode material of lithium and preparation method | |
| CN105174240B (en) | Nanometer rods assembling iron manganese phosphate for lithium microballoon, composite and preparation method thereof | |
| CN106252640A (en) | A kind of mixing polyanionic lithium manganese silicate anode material and preparation method thereof | |
| CN107445210B (en) | High-capacity iron-based lithium ion battery anode material α -LiFeO2Preparation method of (1) | |
| CN104425819B (en) | A kind of preparation method of the ferric metasilicate lithium as anode material for lithium-ion batteries | |
| CN107834070A (en) | A kind of lithium iron phosphate positive material, lithium ion battery and preparation method thereof | |
| CN105355878B (en) | A kind of material as lithium ion cell positive and preparation method thereof | |
| CN111477977B (en) | Water-ether mixed electrolyte for lithium ion battery and preparation method thereof | |
| CN107170976A (en) | A kind of preparation method of cobalt doped lithium titanate nano composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |