CN104692465B - The preparation method of anode material for lithium-ion batteries α-LiFeO2 nano-powder - Google Patents
The preparation method of anode material for lithium-ion batteries α-LiFeO2 nano-powder Download PDFInfo
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- CN104692465B CN104692465B CN201510058684.5A CN201510058684A CN104692465B CN 104692465 B CN104692465 B CN 104692465B CN 201510058684 A CN201510058684 A CN 201510058684A CN 104692465 B CN104692465 B CN 104692465B
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Abstract
The invention discloses a kind of anode material for lithium-ion batteries α-LiFeO
2the preparation method of nano-powder, comprises the steps: that (1) carries the preparation of iron organic phase: in extraction agent and thinner, add ammoniacal liquor, under stirring, add iron nitrate solution, continue to stir extraction, through liquid distributing device separatory, use distilled water wash organic phase, then separatory, collect organic phase; (2) preparation of the aqueous phase lithium aqueous solution; (3) hydrothermal stripping: will carry iron organic phase and the aqueous phase lithium aqueous solution puts into reactor, mixes, sealed reaction; Cooling, centrifugal, precipitation absolute ethanol washing, dry, obtain anode material for lithium-ion batteries α-LiFeO
2nano-powder.Raw material sources of the present invention are wide, and cost is low; Material in production process can be recycled, and without discharge, environmental friendliness: at the end of reaction, isolated organic phase directly can return extraction Fe
3+ion, isolated aqueous phase is treated to be reused; Technique is simple, energy consumption is low.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries α-LiFeO
2nano-powder the preparation method of efficient, energy-conserving and environment-protective.
Background technology
Ferrous acid lithium (LiFeO
2) be a kind of novel lithium battery positive electrode material, there is the advantages such as raw material sources are wide, price is low, environmental protection, LiFeO
2belong to LiMO
2the stratiform transition metal oxide of (M=Fe, Co, Ni, Mn) serial rock salt structure, has higher initial theory specific storage (283mAh/g).At present, the positive electrode material that commercial lithium ion battery uses remains with LiCoO
2be main.But cobalt resource is rare, expensive, biology safety is poor, is not suitable for large-scale application; LiNiO
2structural instability, the cycle performance of battery is bad, poor heat stability, has larger potential safety hazard, in addition LiNiO
2preparation difficulty, is unfavorable for its commercialization; LiMnO
2aboundresources, low price, environmental friendliness, have very large advantage, but in charge and discharge process structural instability, slowly can be transformed into spinel structure, and Jahn-Teller effect easily occurs in spinel structure discharge and recharge between 2.5 ~ 4.3V, cause cycle performance poor, reversible capacity is low.And LiFeO
2as a kind of LiMO
2the positive electrode material of series, has the advantages such as raw material sources are wide, price is low, environmental protection, with LiFePO
4compare, LiFeO
2advantage and using value is had more, therefore LiFeO in resource, price, environmental protection etc.
2it is potential low-cost lithium ion battery anode.
At present, LiFeO
2also certain difficulty is there is, mainly owing to lacking nano-scale LiFeO for anode material for lithium-ion batteries
2high efficiency preparation method.The LiFeO of bibliographical information synthesis so far
2method all have certain defect, the needs of practical application can't be met.Such as, material mixing lack of homogeneity prepared by solid phase method and mechanochemical reaction, the stability of product is bad, batch and batch between the consistence of quality poor, ion exchange method relates to the time-consuming step of the expense energy such as solution weight crystallization and evaporation, and distance practical application also has quite long distance; Hydrothermal method and solvent-thermal method reaction process difficulty control, and raw material range is narrow, and the granularity of synthetic powder is relatively large, and pattern irregularity is unfavorable for the raising of chemical property.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of extraction agent can be recycled, simple, the economical and practical and anode material for lithium-ion batteries α-LiFeO of non-environmental-pollution of preparation technology
2the preparation method of nano-powder.
Technical scheme of the present invention is summarized as follows:
A kind of anode material for lithium-ion batteries α-LiFeO
2the preparation method of nano-powder, comprises the steps:
(1) preparation of iron organic phase is carried: 1-5:1 adds extraction agent and thinner by volume in a reservoir; Adding extraction agent volume 0.1-0.3 massfraction is doubly the ammoniacal liquor of 13%, and under stirring, adding the concentration of iron being equivalent to extraction agent and thinner cumulative volume 2-3 times is 0.05-0.1molL
-1iron nitrate solution, ferrum sulfuricum oxydatum solutum or ferric chloride Solution, continue to stir extraction 0.5-1 hour, through liquid distributing device separatory, use distilled water wash organic phase, then separatory, collect organic phase;
(2) preparation of the aqueous phase lithium aqueous solution: it is 0.1-5molL that lithium hydroxide or lithium nitrate or Lithium Acetate adding distil water are mixed with lithium concentration
-1the lithium aqueous solution;
(3) hydrothermal stripping: be the ratio of 20 ~ 50 in Li/Fe mol ratio, will carry iron organic phase and the aqueous phase lithium aqueous solution puts into reactor, mix, and sealing, reacts 0.5-10 hour under 200-300 DEG C of condition; Naturally cool to room temperature, centrifugal, precipitation absolute ethanol washing 2 ~ 3 times, dry, obtain anode material for lithium-ion batteries α-LiFeO
2nano-powder.
The volume ratio of extraction agent and thinner is preferably 2:1.
The preferred naphthenic acid of extraction agent or tributyl phosphate.
Thinner is preferably C
3-C
8alcohol or kerosene.
0.05-0.1molL
-1iron nitrate solution, ferrum sulfuricum oxydatum solutum or ferric chloride Solution preparation: get the iron nitrate of 0.005-0.01mol, ferric sulfate or iron(ic) chloride and add 90mL distilled water, add the concentrated hydrochloric acid that 2mL massfraction is 36%-38%, stir, then add the H that 1mL massfraction is 30%
2o
2, adding distil water is to 100mL.
Advantage of the present invention:
Raw material sources of the present invention are wide, and cost is low; Material in production process can be recycled, without discharge, pollution-free, environmental friendliness: at the end of reaction, and isolated organic phase directly can return extraction Fe
3+ion, isolated aqueous phase adds a certain amount of LiOHH
2o can reuse; Technique is simple, energy consumption is low.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of product prepared by embodiment 1.
Fig. 2 is the TEM photo of product prepared by embodiment 1.
Fig. 3 is the SEM photo of product prepared by embodiment 1.
Fig. 4 is the XRD figure spectrum of product prepared by embodiment 2.
Fig. 5 is the TEM photo of product prepared by embodiment 2.
Fig. 6 is the SEM photo of product prepared by embodiment 2.
Embodiment
The method of the present invention's application hydrothermal stripping prepares anode material for lithium-ion batteries α-LiFeO
2nano-powder.
First the present invention uses the Fe in organic extractant extraction water solution
3+, then with containing Li
+aqueous phase is by the Fe of load in heat energy back extraction organic phase
3+hydrolysis obtains nanometer α-LiFeO
2powder.Use hydrothermal stripping effectively can control the hydrolysis of metal ion, be conducive to the pattern and the granularity that control product, while low temperature synthetic product, extractant regeneration Reusability, also eliminate the subsequent calcination of other liquid phase method and the process of ball milling, thus achieve production process green, environmental protection and energy-conservation.In addition, " gentleness " of this method by the precipitation process of metal ion being made to become to organic phase metal ion extraction, overcomes the process that direct hydrolysis method is difficult to control precipitation, is convenient to the size of oxide precipitation particle to control in super micrometer range.
Method mechanism
With iron nitrate, LiOHH
2o and naphthenic acid, isooctyl alcohol are that the mechanism of raw material is as follows:
First add by extraction agent naphthenic acid the Fe that thinner isooctyl alcohol comes in extraction water solution
3,
+iron organic phase is carried in preparation, and extraction principle is as follows:
Then make to carry iron organic phase and the aqueous phase lithium aqueous solution (Li/Fe=20 ~ 50) to contact with each other and carry out hydrothermal stripping and obtain α-LiFeO
2throw out, naphthenic acid discharges again and recycles simultaneously, and back extraction principle is as follows:
α-LiFeO
2(aq, crystallized stock)+3RCOOH (org) (recycling)
It is large that the crystallized stock generated forms a nucleus step-length of going forward side by side:
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1
A kind of anode material for lithium-ion batteries α-LiFeO
2the preparation method of nano-powder, comprises the steps:
(1) preparation of iron organic phase is carried: 2:1 adds naphthenic acid and isooctyl alcohol by volume in a reservoir; The massfraction adding naphthenic acid volume 0.3 times is the ammoniacal liquor of 13%, and under stirring, adding the concentration of iron being equivalent to naphthenic acid and isooctyl alcohol cumulative volume 3 times is 0.05molL
-1iron nitrate solution, continue to stir extraction 0.5 hour, through liquid distributing device separatory, use distilled water wash organic phase, then separatory, collect organic phase;
(2) preparation of the aqueous phase lithium aqueous solution: lithium hydroxide adding distil water being mixed with lithium concentration is 1.5molL
-1the lithium aqueous solution;
(3) hydrothermal stripping: be the ratio of 30 in Li/Fe mol ratio, putting into reactor by carrying the aqueous phase lithium aqueous solution that iron organic phase and step (2) obtain, mixing, sealing, reacting 0.5 hour under 230 DEG C of conditions; Naturally cool to room temperature, centrifugal, precipitation absolute ethanol washing 3 times, dry, obtain anode material for lithium-ion batteries α-LiFeO
2nano-powder.
The sign of product
Product 18KW turns target X-ray diffractometer (Rigaku company) measurement result and sees Fig. 1, and in XRD figure spectrum, 2 θ are 37.538 ° (111), 43.626 ° (200), 63.346 ° (220), 75.939 ° (311), 79.867 ° (222) are α-LiFeO
2diffractive features.Under JEM-100C* II type transmission electron microscope (NEC JEOL), observe product pattern and particle diameter are shown in Fig. 2.Under thermal field emission scanning electronic microscope (daily output S-4800), observe product pattern and particle diameter are shown in Fig. 3.
0.05molL
-1the preparation of iron nitrate solution: the iron nitrate getting 0.005mol adds 90mL distilled water, adds the concentrated hydrochloric acid that 2mL massfraction is 36%-38%, stirs, then adds the H that 1mL massfraction is 30%
2o
2, adding distil water is to 100mL.
Embodiment 2
A kind of anode material for lithium-ion batteries α-LiFeO
2the preparation method of nano-powder, comprises the steps:
(1) preparation of iron organic phase is carried: 2:1 adds naphthenic acid and isooctyl alcohol by volume in a reservoir; The massfraction adding naphthenic acid volume 0.3 times is the ammoniacal liquor of 13%, and under stirring, adding the concentration of iron being equivalent to naphthenic acid and isooctyl alcohol cumulative volume 3 times is 0.1molL
-1ferrum sulfuricum oxydatum solutum, continue to stir extraction 0.5 hour, through liquid distributing device separatory, use distilled water wash organic phase, then separatory, collect organic phase;
(2) preparation of the aqueous phase lithium aqueous solution: lithium hydroxide adding distil water being mixed with lithium concentration is 3molL
-1the lithium aqueous solution;
(3) hydrothermal stripping: be the ratio of 28 in Li/Fe mol ratio, will carry iron organic phase and the aqueous phase lithium aqueous solution puts into reactor, mix, sealing, react 6 hours under 220 DEG C of conditions; Naturally cool to room temperature, centrifugal, precipitation absolute ethanol washing 3 times, dry, obtain anode material for lithium-ion batteries α-LiFeO
2nano-powder.
The sign of product
The X-ray diffraction of product is shown in Fig. 4; Fig. 5 is shown in by transmission electron microscope photo.Electron scanning micrograph is shown in Fig. 6.
0.1molL
-1the preparation of ferrum sulfuricum oxydatum solutum: the ferric sulfate getting 0.01mol adds 90mL distilled water, adds the concentrated hydrochloric acid that 2mL massfraction is 36%-38%, stirs, then adds the H that 1mL massfraction is 30%
2o
2, adding distil water is to 100mL.
Embodiment 3
A kind of anode material for lithium-ion batteries α-LiFeO
2the preparation method of nano-powder, comprises the steps:
(1) preparation of iron organic phase is carried: 1:1 adds tributyl phosphate and kerosene by volume in a reservoir; The massfraction adding tributyl phosphate volume 0.1 times is the ammoniacal liquor of 13%, and under stirring, adding the concentration of iron being equivalent to tributyl phosphate and kerosene cumulative volume 2 times is 0.05molL
-1ferric chloride Solution, continue to stir extraction 1 hour, through liquid distributing device separatory, use distilled water wash organic phase, then separatory, collect organic phase;
(2) preparation of the aqueous phase lithium aqueous solution: Lithium Acetate adding distil water being mixed with lithium concentration is 0.1molL
-1the lithium aqueous solution;
(3) hydrothermal stripping: be the ratio of 20 in Li/Fe mol ratio, will carry iron organic phase and the aqueous phase lithium aqueous solution puts into reactor, mix, sealing, react 6 hours under 200 DEG C of conditions; Naturally cool to room temperature, centrifugal, precipitation absolute ethanol washing 2 times, dry, obtain anode material for lithium-ion batteries α-LiFeO
2nano-powder.
X-ray diffraction, the transmission electron microscope photo of product prepared by the present embodiment are similar to the result of embodiment 2 with electron scanning micrograph display.
0.05molL
-1the preparation of ferric chloride Solution: the iron(ic) chloride getting 0.005mol adds 90mL distilled water, adds the concentrated hydrochloric acid that 2mL massfraction is 36%-38%, stirs, then adds the H that 1mL massfraction is 30%
2o
2, adding distil water is to 100mL.
Embodiment 4
A kind of anode material for lithium-ion batteries α-LiFeO
2the preparation method of nano-powder, comprises the steps:
(1) preparation of iron organic phase is carried: 5:1 adds naphthenic acid and Virahol by volume in a reservoir; The massfraction adding naphthenic acid volume 0.3 times is the ammoniacal liquor of 13%, and under stirring, adding the concentration of iron being equivalent to naphthenic acid and Virahol cumulative volume 3 times is 0.1molL
-1iron nitrate solution, continue to stir extraction 1 hour, through liquid distributing device separatory, use distilled water wash organic phase, then separatory, collect organic phase;
(2) preparation of the aqueous phase lithium aqueous solution: lithium nitrate adding distil water being mixed with lithium concentration is 5molL
-1the lithium aqueous solution;
(3) hydrothermal stripping: be the ratio of 50 in Li/Fe mol ratio, will carry iron organic phase and the aqueous phase lithium aqueous solution puts into reactor, mix, sealing, react 10 hours under 300 DEG C of conditions; Naturally cool to room temperature, centrifugal, precipitation absolute ethanol washing 3 times, dry, obtain anode material for lithium-ion batteries α-LiFeO
2nano-powder.
X-ray diffraction, the transmission electron microscope photo of product prepared by the present embodiment are similar to the result of embodiment 2 with electron scanning micrograph display.
0.1molL
-1the preparation of iron nitrate solution: the iron nitrate getting 0.01mol adds 90mL distilled water, adds the concentrated hydrochloric acid that 2mL massfraction is 36%-38%, stirs, then adds the H that 1mL massfraction is 30%
2o
2, adding distil water is to 100mL.
Claims (2)
1. an anode material for lithium-ion batteries α-LiFeO
2the preparation method of nano-powder, is characterized in that comprising the steps:
(1) preparation of iron organic phase is carried: 1-5:1 adds extraction agent and thinner by volume in a reservoir; Adding extraction agent volume 0.1-0.3 massfraction is doubly the ammoniacal liquor of 13%, and under stirring, adding the concentration of iron being equivalent to extraction agent and thinner cumulative volume 2-3 times is 0.05-0.1molL
-1iron nitrate solution, ferrum sulfuricum oxydatum solutum or ferric chloride Solution, continue to stir extraction 0.5-1 hour, through liquid distributing device separatory, use distilled water wash organic phase, then separatory, collect organic phase;
(2) preparation of the aqueous phase lithium aqueous solution: it is 0.1-5molL that lithium hydroxide or lithium nitrate or Lithium Acetate adding distil water are mixed with lithium concentration
-1the lithium aqueous solution;
(3) hydrothermal stripping: be the ratio of 20 ~ 50 in Li/Fe mol ratio, will carry iron organic phase and the aqueous phase lithium aqueous solution puts into reactor, mix, and sealing, reacts 0.5-10 hour under 200-300 DEG C of condition; Naturally cool to room temperature, centrifugal, precipitation absolute ethanol washing 2 ~ 3 times, dry, obtain anode material for lithium-ion batteries α-LiFeO
2nano-powder; Described extraction agent is naphthenic acid or tributyl phosphate; Described thinner is C
3-C
8alcohol or kerosene.
2. a kind of anode material for lithium-ion batteries α-LiFeO according to claim 1
2the preparation method of nano-powder, is characterized in that the volume ratio of extraction agent and thinner is 2:1.
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| CN105236494A (en) * | 2015-10-19 | 2016-01-13 | 天津大学 | Method for synthesizing alpha-LiFeO2 nanoparticles in one-step mode with Qinghai salt lake brine as raw material |
| CN105591095A (en) * | 2016-02-27 | 2016-05-18 | 东莞市迈科科技有限公司 | Preparation method of nano powder of lithium-rich manganese-based positive electrode material of lithium battery |
| CN106241881B (en) * | 2016-07-15 | 2018-07-20 | 天津大学 | A kind of electro-chemical activity β-LiFe5O8The preparation method of nano-particle |
| CN107445210B (en) * | 2017-07-03 | 2020-03-27 | 电子科技大学 | High-capacity iron-based lithium ion battery anode material α -LiFeO2Preparation method of (1) |
| CN109852797B (en) * | 2017-12-16 | 2020-12-29 | 虔东稀土集团股份有限公司 | Extraction solvent for extracting and separating lithium element and method for extracting and separating lithium element by using extraction solvent |
| CN110048120B (en) * | 2019-04-23 | 2020-09-25 | 王柯娜 | Preparation method of nano lithium ferrite |
| CN112408354A (en) * | 2020-11-19 | 2021-02-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of lithium iron phosphate cathode material |
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| JP2931961B2 (en) * | 1996-08-27 | 1999-08-09 | 工業技術院長 | Method for producing layered rock-salt type lithium ferrite by solvothermal ion exchange method |
| JP2855190B2 (en) * | 1996-11-13 | 1999-02-10 | 工業技術院長 | Production method of layered rock salt type lithium ferrite by mixed alkaline hydrothermal method |
| JP3837469B2 (en) * | 2001-05-21 | 2006-10-25 | 独立行政法人産業技術総合研究所 | Layered rock salt type lithium iron oxide and method for producing the same |
| CN101393984A (en) * | 2008-11-06 | 2009-03-25 | 上海交通大学 | Positive electrode material of Lithium ion battery and producing process thereof |
| CN103560237B (en) * | 2013-11-08 | 2015-10-28 | 安泰科技股份有限公司 | A kind of nanometer iron-lithium oxide composite negative electrode material and preparation method thereof |
| CN103956461B (en) * | 2014-04-28 | 2016-06-15 | 张家港智电芳华蓄电研究所有限公司 | A kind of hydrothermal preparing process of LiFePO 4 and ferrous acid lithium composite material |
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