CN100418256C - ZnO coated surface spinel type LiMnO positive electrode material and its preparation method - Google Patents
ZnO coated surface spinel type LiMnO positive electrode material and its preparation method Download PDFInfo
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- CN100418256C CN100418256C CNB2006100214862A CN200610021486A CN100418256C CN 100418256 C CN100418256 C CN 100418256C CN B2006100214862 A CNB2006100214862 A CN B2006100214862A CN 200610021486 A CN200610021486 A CN 200610021486A CN 100418256 C CN100418256 C CN 100418256C
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- China
- Prior art keywords
- limn
- spinel
- preparation
- zinc acetate
- electrode material
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- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000007774 positive electrode material Substances 0.000 title description 2
- 229910052596 spinel Inorganic materials 0.000 title description 2
- 239000011029 spinel Substances 0.000 title description 2
- 229910014689 LiMnO Inorganic materials 0.000 title 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004246 zinc acetate Substances 0.000 claims abstract description 12
- 229910015645 LiMn Inorganic materials 0.000 claims description 35
- 239000000843 powder Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 3
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 abstract 3
- 229910014135 LiMn2 O4 Inorganic materials 0.000 abstract 1
- 239000010405 anode material Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000003349 gelling agent Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- -1 lithium boron oxide compound Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a method for covering ZnO particle on the surface of LiMn2O4, wherein it comprises: mixing zinc acetate with gelling agent; adding LiMn2 O4; mixing to obtain dry gel; drying the gel in 10-250Deg. C for 1-24hours to obtain the predecessor; sintering it for 1-24hours at 300-1000Deg. C, to obtain the LiMn2O4 anode material with different contents of ZnO covered. The invention can reduce the contact area between anode and electrolyte, to improve the high-temperature (55Deg. C) cycle property of LiMn2O4, with lower cost.
Description
Technical field
The invention belongs to a kind of anode active material of lithium ion battery through modification, particularly at the LiMn of surperficial clading ZnO
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), the 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 not very clear, 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
4Heat endurance 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 in recent years inchoate.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., the .[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 State Ionics 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);
Through the LiMn after the surface treatment
2O
4Positive electrode can reduce contacting of positive electrode and electrolyte to a certain extent, reduces the dissolving of Mn, thereby improves LiMn
2O
4High temperature cyclic performance.This shows that the surface coats processes for suppressing LiMn
2O
4The high temperature capacity attenuation of positive electrode has certain effect.
Summary of the invention
For LiMn
2O
4Mn dissolving and the decomposition of electrolyte all occur in this fact of electrode material surface, the present invention adopts common metal oxide ZnO as clad material, neither affect the embedding of positive electrode lithium ion in charge and discharge process and take off embedding, can reduce the contact area of material and electrolyte again, thereby reach LiMn
2O
4Carry out the effect of surface modification treatment.
The present invention has following characteristics: (1) a certain amount of ZnO coats rear to former positive electrode LiMn
2O
4Not impact of structure; (2) amount that coats can be controlled flexibly by changing technological parameter; (3) raw material that uses 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 high temperature (55 ℃) cyclical stability is significantly improved.
Embodiment of the present invention:
(1) zinc acetate that will necessarily measure under agitation is dissolved in absolute ethyl alcohol or the deionized water, slowly drips a certain amount of complexing agent again, and wherein the mol ratio of metal ion and complexing agent is: 0.02-5: 1, become faint yellow vitreosol liquid behind the stirring certain hour;
(2) above-mentioned sol liquid stirring after 10～90 minutes, is pressed different proportion and added spinel-type LiMn
2O
4, wherein zinc acetate and spinel-type LiMn
2O
4Mass ratio be: 2.7-13.5: 100, in 50～100 ℃ lower continue to stir became Gel Precursor in 1～24 hour;
(3) presoma is changed in the baking oven 25-200 ℃ dry 1-24 hour down, become dry gel powder;
(4) dry gel powder is put into Muffle furnace and carried out high-temperature heat treatment, temperature maintenance is at 300-1000 ℃, and heat treatment time is 1-48 hour, is down to then room temperature, obtains the spinel-type LiMn of different coating ratios
2O
4Positive electrode active materials.
Description of drawings
LiMn before Fig. 1 (a) coats
2O
4The XRD collection of illustrative plates; (b) press the LiMn that embodiment 1 prepared 1wt%ZnO coats
2O
4The XRD collection of illustrative plates; (c) press embodiment 2 prepared 2wt%ZnO and coat LiMn
2O
4The XRD collection of illustrative plates and (d) press the prepared 5wt%ZnO coating of embodiment 3 LiMn
2O
4The XRD collection of illustrative plates.
The 1wt%ZnO that Fig. 2 presses embodiment 1 preparation coats LiMn
2O
4The XPS collection of illustrative plates of material surface Zn element.
LiMn before Fig. 3 coats
2O
4With according to embodiment 1, LiMn after 1wt%, the 2wt%ZnO of example 2 preparation coats
2O
4Under 55 ℃ with the charging and discharging curve of 0.5C multiplying power.
LiMn before Fig. 4 coats
2O
4With according to embodiment 1, LiMn after 1wt%, the 2wt%ZnO of example 2 preparation coats
2O
4Under 55 ℃ with the cyclic curve of 0.5C multiplying power.
Embodiment
Embodiment 1:
Analyze pure zinc acetate 0.3356g and under agitation join in the 5ml absolute ethyl alcohol, treat that zinc acetate dissolves fully after, stir the lower 1.5ml triethanolamine solution that slowly drips, form faint yellow vitreosol.Stir after 30 minutes, add 9.9gLiMn
2O
4Powder stirred 4 hours 80 ℃ of lower continuation then, and colloidal sol becomes the black gelatinous mixture gradually.Gel mixture is put into the oven dry of 150 ℃ of baking ovens spend the night, become the black dry gel powder, with the directly 500 ℃ of roastings 5 hours in Muffle furnace of this dry gel powder, naturally be down to room temperature, get the LiMn of 1wt%Zn coating
2O
4Powder.
Embodiment 2:
Analyze pure zinc acetate 0.6709g and under agitation join in the 10ml absolute ethyl alcohol, treat that zinc acetate dissolves fully after, stir the lower 2.0ml triethanolamine solution that slowly drips, form faint yellow vitreosol.Stir after 30 minutes, add 9.8gLiMn
2O
4Powder stirred 4 hours 80 ℃ of lower continuation then, and colloidal sol becomes the black gelatinous mixture gradually.Gel mixture is put into the oven dry of 150 ℃ of baking ovens spend the night, become the black dry gel powder, with the directly 500 ℃ of roastings 5 hours in Muffle furnace of this dry gel powder, naturally be down to room temperature, get the LiMn of 2wt%Zn coating
2O
4Powder.
Embodiment 3:
Analyze pure zinc acetate 1.6781g and under agitation join in the 15ml absolute ethyl alcohol, treat that zinc acetate dissolves fully after, stir the lower 2.5ml triethanolamine solution that slowly drips, form faint yellow vitreosol.Stir after 30 minutes, add 9.5gLiMn
2O
4Powder stirred 4 hours 80 ℃ of lower continuation then, and colloidal sol becomes the black gelatinous mixture gradually.Gel mixture is put into the oven dry of 150 ℃ of baking ovens spend the night, become the black dry gel powder, with the directly 500 ℃ of roastings 5 hours in Muffle furnace of this dry gel powder, naturally be down to room temperature, get the LiMn of 5wt%Zn coating
2O
4Powder.
Claims (2)
1. the spinel-type LiMn of a surperficial clading ZnO
2O
4The preparation method of electrode material is characterized in that:
(1) zinc acetate under agitation is dissolved in absolute ethyl alcohol or the deionized water, and then slowly drips a certain amount of complexing agent, wherein the mol ratio of zinc acetate and complexing agent is: 0.02-5: 1;
The sol liquid that (2) will be obtained by step (1) stirred after 10～90 minutes, press different proportion adding spinel-type LiMn
2O
4, wherein zinc acetate and spinel-type LiMn
2O
4Mass ratio be: 2.7-13.5: 100, in 50～100 ℃ lower continue to stir became Gel Precursor in 1～24 hour;
(3) presoma is changed in the baking oven 25-200 ℃ dry 1-24 hour down, become dry gel powder;
(4) dry gel powder is put into Muffle furnace and carried out high-temperature heat treatment, temperature maintenance is at 300-1000 ℃, and heat treatment time is 1-48 hour, reduces to room temperature then.
2. according to the spinel-type LiMn of the described surperficial clading ZnO of claim 1
2O
4The preparation method of electrode material is characterized in that: described complexing agent is selected triethanolamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100214862A CN100418256C (en) | 2006-07-28 | 2006-07-28 | ZnO coated surface spinel type LiMnO positive electrode material and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100214862A CN100418256C (en) | 2006-07-28 | 2006-07-28 | ZnO coated surface spinel type LiMnO positive electrode material and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1909270A CN1909270A (en) | 2007-02-07 |
| CN100418256C true CN100418256C (en) | 2008-09-10 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100214862A Expired - Fee Related CN100418256C (en) | 2006-07-28 | 2006-07-28 | ZnO coated surface spinel type LiMnO positive electrode material and its preparation method |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102315430B (en) * | 2011-10-21 | 2013-06-05 | 佛山市邦普循环科技有限公司 | Preparation method for metallic oxide cladded anode material of lithium ion battery |
| CN103022470B (en) * | 2012-12-19 | 2016-01-20 | 苏州大学 | AZO coating LiMn 2 O positive pole material of secondary lithium battery and preparation method thereof |
| CN102983324B (en) * | 2012-12-19 | 2015-07-15 | 苏州大学 | Positive material of AZO-coated lithium nickel manganese oxide secondary lithium battery and preparation method of positive pole material |
| CN104752710B (en) * | 2015-03-11 | 2018-01-19 | 云南民族大学 | One kind cladding ZnO positive electrodes LiMn2O4Fast preparation method |
| CN104733714B (en) * | 2015-03-25 | 2017-04-12 | 中国科学院化学研究所 | Modification method of lithium ion battery cathode material |
| CN106099047A (en) * | 2016-08-25 | 2016-11-09 | 深圳市贝特瑞纳米科技有限公司 | A kind of surface coating method of electrode material and application thereof |
| CN110661033B (en) * | 2018-06-28 | 2021-06-22 | 宁德时代新能源科技股份有限公司 | Ion exchange material, preparation method thereof, electrolyte film and secondary battery |
| CN110224137B (en) * | 2019-05-28 | 2022-06-24 | 中南大学 | Method for directionally constructing interface modification layer of manganese-containing material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08236114A (en) * | 1995-02-27 | 1996-09-13 | Sanyo Electric Co Ltd | Lithium secondary battery |
| CN1725534A (en) * | 2004-07-22 | 2006-01-25 | 日本化学工业株式会社 | Modified li-Mg-Ni composite oxides and manufacturing method, Li secondary battery and positive electrode active material |
-
2006
- 2006-07-28 CN CNB2006100214862A patent/CN100418256C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08236114A (en) * | 1995-02-27 | 1996-09-13 | Sanyo Electric Co Ltd | Lithium secondary battery |
| CN1725534A (en) * | 2004-07-22 | 2006-01-25 | 日本化学工业株式会社 | Modified li-Mg-Ni composite oxides and manufacturing method, Li secondary battery and positive electrode active material |
Non-Patent Citations (4)
| Title |
|---|
| Enhanced low voltage cycling stability of LiMn2O4 cathodeby ZnO coating for lithium ion batteries. J. Tu, X.B. Zhao, et al.Journal of Alloys and Compounds,Vol.432 . 2006 |
| Enhanced low voltage cycling stability of LiMn2O4 cathodeby ZnO coating for lithium ion batteries. J. Tu, X.B. Zhao, et al.Journal of Alloys and Compounds,Vol.432 . 2006 * |
| 非均匀成核法表面包覆氧化铝的尖晶石LiMn2O4研究. 王志兴等.物理化学学报，第20卷第8期. 2004 |
| 非均匀成核法表面包覆氧化铝的尖晶石LiMn2O4研究. 王志兴等.物理化学学报，第20卷第8期. 2004 * |
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| CN1909270A (en) | 2007-02-07 |
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