CN100364153C - Li4Ti5O12 cathode material cladden on surface of spinel LiMn2O4 and preparation method thereof - Google Patents
Li4Ti5O12 cathode material cladden on surface of spinel LiMn2O4 and preparation method thereof Download PDFInfo
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- CN100364153C CN100364153C CNB2005100209408A CN200510020940A CN100364153C CN 100364153 C CN100364153 C CN 100364153C CN B2005100209408 A CNB2005100209408 A CN B2005100209408A CN 200510020940 A CN200510020940 A CN 200510020940A CN 100364153 C CN100364153 C CN 100364153C
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- lithium
- limn2o4
- li4ti5o12
- ion battery
- mixed liquid
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to Li4Ti5O12 coated on the surface of LiMn2O4, and a preparation method thereof. The method comprises the following steps that compounds with lithium and titanium are mixed and stirred for a certain time under the action of gelling agents, LiMn2O4 is added, and the mixture is stirred for a certain time to form dried gel which is baked for 1 to 24 hours at a temperature of 10 to 250 DEG C to form precursors; the precursors are sintered for 5 to 24 hours in air at a temperature of 300 to 900DEGC to obtain different LiMn2O4 electrode materials with a different amount of coating content. Because the present invention considers Li4Ti5O12 zero straining structure, and utilizes the high Li<+> diffusion coefficient of Li4Ti5O12, the present invention effectively reduces the capacity loss resulting from LiMn2O4 solution, and not only enhances the cycle performance of LiMn2O4, but also has a little influence on the cycle performance in the process of 10C heavy current charge and discharge; the present invention has the advantages of simple synthesis technology, low cost, and easy implementation in industry.
Description
Technical field
The invention belongs to a kind of anode active material of lithium ion battery, particularly coat Li on the surface through modification
4Ti
5O
12LiMn
2O
4And preparation method thereof.
Background technology
Since lithium ion battery in 1991 came out, its positive electrode was the focus of research always.The positive electrode of commercial applications is stratiform LiCoO at present
2Though, it have open circuit voltage height, specific energy big, have extended cycle life, can repid discharge etc. advantage, exist cost an arm and a leg, problem such as environmental pollution, substitute LiCoO so need to seek a kind of energy
2Positive electrode.Wherein, the LiMn of spinel structure
2O
4Has higher operating voltage (about 3.9V vs.Li
+/ Li), characteristics such as cheap, environmentally friendly, so be considered to be hopeful most substitute LiCoO
2One of first-selected positive electrode.But in commercialization process, also have following problems to wait to solve: (1) Reversible Cycle capacity on the low side (110~130mAh/g); (2) capacitance loss is serious under the high temperature.Wherein, LiMn
2O
4The high temperature capacitance loss be to hinder one of its business-like key factor.And cause LiMn
2O
4The reason of high temperature capacity attenuation is still very not clear and definite, mainly contains following several explanation: (1) Mn melts; (2) electrolyte decomposition; (3) Jahn-Teller distortion.In order to solve fast this international difficult problem of capacity attenuation, the scientific research group of various countries is to LiMn
2O
4Thermal stability further investigate, and material is carried out modification.In recent years, for LiMn
2O
4Study on the modification mainly concentrate on and mix and the surface coats, the more and surface coated research of the research of wherein mixing is inchoate in recent years.At present, the LiMn that has reported both at home and abroad
2O
4The surface comprises:
1. utilize lithium boron oxide compound (LBO) and acetylacetone,2,4-pentanedione (acetylacetone) to LiMn
2O
4Carry out surface treatment (Amatucci G.G, Blyr A. .[J such as Sigala C.] Solid State Ionics, 1997,104:13-25);
2. at LiMn
2O
4Surface coating layer shape LiCoO
2(Park S.C., Kim Y.M., [J] .Journal ofPower Sources such as Kang Y.M., 2001,103:86-92; Shu D, Kumar G, [J] Solid StateIonics such as Kim K B., 2003,160:227-233);
3. Al
2O
3The surface coating (Lee S-W, Kim K-S, Moon H-S etc., [J] Journal of Power Sources, 2004,126:150-155);
4. MgO surface coating (Gedanken A waits [J] Electrochemistrycommunications for Gnanaraj J.S, Pol V G, and 2003,5:940-945);
5. SiO
2The surface coating (Zheng Z.S, Tang Z.L .[J such as Zhang Z.T] Solid State Ionics, 2002,148:317-321);
More than coat, except LiCoO
2Have higher chemical diffusion coefficient, outside the electronic conductivity, other clad materials all have weak point, and then have influence on LiMn
2O
4Chemical property.
Summary of the invention
At above weak point, consider Li
4Ti
5O
12Itself can be used as electrode material, and has the LiMn of ratio
2O
4Higher chemical diffusion coefficient and electronic conductivity, and Li
4Ti
5O
12Also have and LiMn
2O
4The same spinel structure, simultaneously, Li
4Ti
5O
12Structure does not change in the charge/discharge process, is a kind of " zero strain " material, does not influence the stability of material.Thereby the present invention adopts Li
4Ti
5O
12As clad material, to LiMn
2O
4Carry out surface modification treatment.
The present invention has following characteristics: (1) coats the structure not influence of back to former product; (2) amount of Bao Fuing can be controlled flexibly by changing technological parameter; (3) raw material of Shi Yonging all is common industrial chemicals, and is cheap, pollution-free, security performance is good; (4) coating process is simple, and flow process is short, and is easy to control; (5) material after the coating is assembled into test cell, and cyclical stability is significantly improved.
The invention process step:
(1) lithium acetate under agitation is dissolved in the mixed liquid that contains absolute ethyl alcohol, deionized water, complexing agent, wherein absolute ethyl alcohol: deionized water: the complexing agent volume ratio is (1-50): (1-5): (1-5);
(2) the above-mentioned mixed liquid of lithium that contains is dropwise joined in the titaniferous solution of stirring, become the vitreosol that contains lithium, titanium, wherein Li: the Ti mol ratio is 4: 5;
(3) contain lithium, the stirring of titanium colloidal sol after 30 minutes with above-mentioned, press different proportion and add spinelle LiMn
2O
4, continue stirring and became Gel Precursor in 1-24 hour;
(4) presoma is changed in the baking oven in 25-200 ℃ dry 1-24 hour down, become dry gel powder;
(5) dry gel powder is put into Muffle furnace and carried out high-temperature heat treatment, temperature maintenance is at 500-1000 ℃, and heat treatment time is 10-48 hour, reduces to room temperature then, obtains the final sample of different coating ratios.
Description of drawings
Fig. 1 is according to the Li that the present invention relates to the method preparation
4Ti
5O
12The XRD figure spectrum of sample.
LiMn before Fig. 2 (a) coats
2O
4And (b) compare Li by embodiment 1 prepared 1%mol
4Ti
5O
12The LiMn that coats
2O
4Powder X-ray RD collection of illustrative plates.
LiMn before Fig. 3 (a) coats
2O
4With press embodiment 1-example 3 prepared (b) 1%, (c) 2%, (d) 3% mol ratio Li
4Ti
5O
12LiMn after the coating
2O
4The first charge-discharge curve.
Fig. 4 coats preceding LiMn
2O
4With according to embodiment 1-example 3 preparation 1%, 2%, 3% mol ratio Li
4Ti
5O
12LiMn after the coating
2O
4Preceding 20 charge and discharge cycles test results.
Embodiment
Embodiment 1:
Lithium acetate 0.2303g under agitation joins in the 2ml absolute ethyl alcohol, in the mixed solution of 0.25ml deionized water, 0.2ml glacial acetic acid, after lithium acetate dissolves fully, stir down and slowly transfer in the 0.9701g metatitanic acid fourth lipoprotein solution, form faint yellow vitreosol, stir after 30 minutes, add 10gLiMn
2O
4Powder continue to stir 4 hours, and colloidal sol becomes gel gradually, gel is put into 150 ℃ of baking ovens oven dry spend the night, and became dry gel powder, with the direct 800 ℃ of sintering 24 hours in Muffle furnace of this dry gel powder, reduced to room temperature naturally, must 1%molLi
4Ti
5O
12The LiMn that coats
2O
4Powder.
Embodiment 2:
Lithium acetate 0.2326g under agitation joins in the 3ml absolute ethyl alcohol, in the mixed solution of 0.28ml deionized water, 0.25ml glacial acetic acid, after lithium acetate dissolves fully, stir down and slowly transfer in the 0.9800g metatitanic acid fourth lipoprotein solution, form faint yellow vitreosol, stir after 30 minutes, add 5gLiMn
2O
4Powder continue to stir 4 hours, and colloidal sol becomes gel gradually, gel is put into 150 ℃ of baking ovens oven dry spend the night, and became dry gel powder, with the direct 800 ℃ of sintering 24 hours in Muffle furnace of this dry gel powder, reduced to room temperature naturally, must 2%molLi
4Ti
5O
12The LiMn that coats
2O
4Powder.
Embodiment 3:
Lithium acetate 0.2115g under agitation joins in the 3.1ml absolute ethyl alcohol, in the mixed solution of 0.23ml deionized water, 0.2ml glacial acetic acid, after lithium acetate dissolves fully, stir down and slowly transfer in the 0.8911g metatitanic acid fourth lipoprotein solution, form faint yellow vitreosol, stir after 30 minutes, add 3gLiMn
2O
4Powder continue to stir 4 hours, and colloidal sol becomes gel gradually, gel is put into 150 ℃ of baking ovens oven dry spend the night, and became dry gel powder, with the direct 800 ℃ of sintering 24 hours in Muffle furnace of this dry gel powder, reduced to room temperature naturally, must 3%molLi
4Ti
5O
12The LiMn that coats
2O
4Powder.
Claims (6)
1. spinelle LiMn
2O
4The surface coats Li
4Ti
5O
12The electrode material preparation method is characterized in that:
(1) lithium acetate under agitation is dissolved in the mixed liquid that contains absolute ethyl alcohol, deionized water, glacial acetic acid, wherein absolute ethyl alcohol: deionized water: the glacial acetic acid volume ratio is (1-50): (1-5): (1-5);
(2) the above-mentioned mixed liquid of lithium that contains is dropwise joined in the metatitanic acid fourth fat of stirring, become the vitreosol that contains lithium, titanium, wherein Li: the Ti mol ratio is 4: 5;
(3) contain lithium, the stirring of titanium colloidal sol after 30 minutes with above-mentioned, press different proportion and add spinelle LiMn
2O
4, continue stirring and became Gel Precursor in 1-24 hour;
(4) presoma is changed in the baking oven 25-200 ℃ dry 1-24 hour down, become dry gel powder;
(5) dry gel powder is put into Muffle furnace and carried out high-temperature heat treatment, temperature maintenance is at 500-1000 ℃, and heat treatment time is 10-48 hour, reduces to room temperature then.
2. method prepares spinelle LiMn according to claim 1
2O
4The lithium ion battery of electrode material comprises positive electrode, negative material, electrolyte, barrier film, it is characterized in that described positive electrode comprises: the surface coats different molar content Li
4Ti
5O
12Spinelle LiMn
2O
4Positive active material, conductive agent and binding agent; Three's quality percentage composition is respectively: 93-70%, 4-20%, 3-10%.
3. as lithium ion battery as described in the claim 2, it is characterized in that described negative pole is a lithium metal.
4. as lithium ion battery as described in the claim 2, it is characterized in that described electrolyte is to contain the lithium salts of 1mol/L and the mixed liquid of organic solvent, wherein lithium salts is selected lithium hexafluoro phosphate for use; Organic solvent is selected the mixed liquid of ethylene carbonate and diethyl carbonate for use, and the two volume ratio is 1: 1; Or the mixed liquid of ethylene carbonate and diethyl carbonate and dimethyl carbonate, three's volume ratio is 1: 1: 1.
5. the described lithium ion battery of claim 2 is characterized in that described barrier film is porous polyethylene film or porousness polypropylene screen.
6. as lithium ion battery as described in the claim 2, it is characterized in that described conductive agent selects acetylene black for use; Binding agent is selected polytetrafluoroethylene for use, or Kynoar.
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Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102007030604A1 (en) * | 2007-07-02 | 2009-01-08 | Weppner, Werner, Prof. Dr. | Ion conductor with garnet structure |
CN102315449B (en) * | 2011-08-10 | 2013-12-04 | 东莞市迈科科技有限公司 | Composite material Li3V2(PO4)3/Li4Ti5O12 and preparation method thereof |
CN103594682A (en) * | 2013-10-23 | 2014-02-19 | 江苏大学 | Preparation method of lithium ion battery solid solution positive pole material |
CN103594683B (en) * | 2013-11-13 | 2015-08-05 | 北京理工大学 | A kind of coating modification method preparing high temp. lithium ion battery manganate cathode material for lithium |
CN103606673B (en) * | 2013-11-14 | 2016-07-20 | 江苏大学 | A kind of preparation method of laminar-spinel compound sosoloid anode material |
CN104347880A (en) * | 2014-10-14 | 2015-02-11 | 东莞新能源科技有限公司 | Lithium ion battery capable of quick charging |
CN107768657A (en) * | 2017-11-10 | 2018-03-06 | 贵州丕丕丕电子科技有限公司 | A kind of anode material for lithium-ion batteries, preparation method and lithium ion battery |
Citations (6)
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JP2001192208A (en) * | 1999-06-03 | 2001-07-17 | Titan Kogyo Kk | Lithium-titanium multiple oxide, its manufacturing method and its use |
CN1326232A (en) * | 2000-05-25 | 2001-12-12 | 中国科学院成都有机化学研究所 | Process for preparing lithium manganese oxide as positive electrode of lithium ion battery |
US20020182504A1 (en) * | 2001-05-31 | 2002-12-05 | Naoki Imachi | Nonaqueous electrolyte secondary battery |
CN1389939A (en) * | 2001-06-04 | 2003-01-08 | 中国科学院成都有机化学研究所 | Method of synthesizing LiCo1-xMxO2 as positive electrode material for lithium ion accmulator |
US20040197657A1 (en) * | 2001-07-31 | 2004-10-07 | Timothy Spitler | High performance lithium titanium spinel li4t15012 for electrode material |
CN1610152A (en) * | 2003-10-17 | 2005-04-27 | 胡祥 | Lithium ion secondary cells positive pole active material and producing method |
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- 2005-05-24 CN CNB2005100209408A patent/CN100364153C/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001192208A (en) * | 1999-06-03 | 2001-07-17 | Titan Kogyo Kk | Lithium-titanium multiple oxide, its manufacturing method and its use |
CN1326232A (en) * | 2000-05-25 | 2001-12-12 | 中国科学院成都有机化学研究所 | Process for preparing lithium manganese oxide as positive electrode of lithium ion battery |
US20020182504A1 (en) * | 2001-05-31 | 2002-12-05 | Naoki Imachi | Nonaqueous electrolyte secondary battery |
CN1389939A (en) * | 2001-06-04 | 2003-01-08 | 中国科学院成都有机化学研究所 | Method of synthesizing LiCo1-xMxO2 as positive electrode material for lithium ion accmulator |
US20040197657A1 (en) * | 2001-07-31 | 2004-10-07 | Timothy Spitler | High performance lithium titanium spinel li4t15012 for electrode material |
CN1610152A (en) * | 2003-10-17 | 2005-04-27 | 胡祥 | Lithium ion secondary cells positive pole active material and producing method |
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