CN102916173A - Preparation method of modified lithium manganate anode material of lithium ion battery - Google Patents
Preparation method of modified lithium manganate anode material of lithium ion battery Download PDFInfo
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- CN102916173A CN102916173A CN2012103934269A CN201210393426A CN102916173A CN 102916173 A CN102916173 A CN 102916173A CN 2012103934269 A CN2012103934269 A CN 2012103934269A CN 201210393426 A CN201210393426 A CN 201210393426A CN 102916173 A CN102916173 A CN 102916173A
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- preparation
- ion battery
- lithium ion
- zirconia
- lithium manganate
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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
Abstract
The invention discloses a preparation method of a modified lithium manganate anode material of a lithium ion battery. The preparation method comprises the following steps of: dissolving KMnO4 and an ammonium salt in distilled water to form a uniformly mixed solution, and reacting at constant temperature to obtain a manganese dioxide nanometer material; uniformly mixing the manganese dioxide nanometer material, titanium oxide and lithium carbonate, and sintering to obtain LiMn2-xTixO4 particles; and fusing the LiMn2-xTixO4 particles, boric hydroxide as a fusion agent and zirconia, and processing at high temperature to obtain the modified lithium manganate anode material with a zirconia-cladded surface. According to the anode material of the lithium ion battery, prepared according to the invention, the Ti-doped lithium manganate material is adopted and is uniformly cladded with the zirconia material, so that while the high specific capacity is achieved, a good charge/discharge performance is achieved, and the anode material has a good cyclic stability event at high temperature and is high in specific capacity, good in high-temperature property and long in service life when applied to the lithium ion battery.
Description
Technical field
The present invention relates to a kind of preparation method of anode material for lithium ion battery, relate in particular to a kind of lithium ion battery with modified lithium manganate cathode material, and preparation method thereof.
Background technology
Lithium ion battery is as a kind of novel secondary cell, has specific capacity height, voltage is high, fail safe is good characteristics, is widely used in the driving power of electric automobile, mobile phone, notebook computer.During critical material during positive electrode in the lithium ion battery, the lithium ion battery of being used widely at present, its positive electrode are just experiencing constantly renewal and are improveing.
LiMn2O4 has plurality of advantages as anode material for lithium-ion batteries: (1) bulk effect is good; (2) require low to over-charge protective; (3) have unique three-dimensional ionic transport passages, be conducive to lithium ion and in crystal, spread, be fit to be applied in the field of high-power fast charging and discharging.In view of these advantages, LiMn2O4 is become be hopeful one of positive electrode of substituting cobalt acid lithium most.But because the LiPF in the electrolyte
6And H
2The HF that the O reaction produces lures Mn into
3+Disproportionated reaction occuring, cause occuring the decay of capacity in cyclic process, particularly shows particularly outstandingly when high temperature, and aggravate along with the rising of temperature, thereby limited its commercial applications.
Adopt the method for surface coating modification, can improve this state, be about to the surface that clad material is coated on lithium manganate particle, minimizing electrolyte contacts with LiMn2O4, thereby suppresses the dissolving of manganese, the corresponding high temperature circulation stability that improves manganate cathode material for lithium.
Summary of the invention
The purpose of this invention is to provide a kind of lithium ion battery with the preparation method of modified lithium manganate cathode material, the characteristics such as use that the lithium ion battery of the anode composite material of the method preparation has that specific capacity is large, high temperature safe performance and high temperature cyclic performance are good.
To achieve these goals, a kind of lithium ion battery provided by the invention comprises the steps: with the preparation method of modified lithium manganate cathode material
Step 1, the preparation in manganese source: get 2-4mol KMnO
4Be dissolved into the 2-4mol ammonium salt and form homogeneous mixture solotion in the distilled water, at 120-150 ℃ of lower isothermal reaction 6-10h, be cooled to again room temperature, collecting precipitation, through deionized water and absolute ethanol washing, drying gets nano material of manganese dioxide;
Step 2, preparation LiMn
2-xTi
xO
4Particle: with above-mentioned nano material of manganese dioxide, titanium oxide and lithium carbonate Li in molar ratio
:Mn
:Ti=1
:(2-x)
:(x), adopt ball-milling method to mix after, then broken with 900 ℃-1100 ℃ temperature under argon gas atmosphere sintering 10-20 hour, obtain LiMn
2-xTi
xO
4Particle, wherein 0.1≤x≤0.2;
Step 3 coats zirconia: with described LiMn
2-xTi
xO
4Particle, melting agent boron hydroxide and zirconia are according to mol ratio 1
:(0.2-0.3)
:(0.06-0.08) mix, join in the middle of the fusion device, fusion temperature is 500-700 ℃, and adjusting rotary speed is 6000-6500rpm, and time of fusion is 2-3h; Taking-up is placed under 900-1000 ℃, and constant temperature 6-8h is cooled to room temperature acquisition surface and is coated with zirconic modified lithium manganate cathode material.
Wherein, drying condition is preferably described in the step 1: 70-90 ℃ of lower heating, drying 11-13h.
Wherein, ammonium salt described in the step 1 is preferably and is selected from NH
4NO
3, NH
4Cl most preferably is NH
4NO
3
Second purpose of the present invention provides a kind of lithium ion battery modified lithium manganate cathode material of above-mentioned any means preparation.
The anode material for lithium-ion batteries of the present invention's preparation, adopted the lithium manganate material of the Ti that mixed, and evenly coated zirconia material, therefore when having height ratio capacity, charge-discharge performance is good, also has good cyclical stability under high-temperature condition, when being used for lithium ion battery, specific capacity is high, and high-temperature behavior is good, long service life.
Embodiment
Embodiment one
The preparation in manganese source
Get 2mol KMnO
4With 2mol NH
4NO
3Be dissolved in the distilled water and form homogeneous mixture solotion and join in the polytetrafluoroethylene hydrothermal reaction kettle, at 120 ℃ of lower isothermal reaction 10h, naturally cool to again room temperature, fully wash through deionized water and absolute ethyl alcohol, 70 ℃ of lower heating, drying 13h get nano material of manganese dioxide.
Preparation LiMn
1.9
Ti
0.1
O
4
Particle
With above-mentioned nano material of manganese dioxide, titanium oxide and lithium carbonate Li in molar ratio
:Mn
:Ti=1
:1.9
:0.1, adopt ball-milling method to mix after, with 900 ℃ temperature sintering 20 hours under argon gas atmosphere, then broken, classification obtains LiMn
1.9Ti
0.1O
4Particle.
Coat zirconia
With described LiMn
1.9Ti
0.1O
4Particle, melting agent boron hydroxide and zirconia are according to mol ratio 1
:0.2
:0.06 mix, join in the middle of the fusion device, fusion temperature is 500 ℃, adjusting rotary speed is 6000rpm, and time of fusion is 3h, puts into Muffle furnace after the taking-up, the temperature that Muffle furnace is set is 900 ℃, and constant temperature 8h is cooled to room temperature acquisition surface and is coated with zirconic modified lithium manganate cathode material.
Embodiment two
The preparation in manganese source
Get 4mol KMnO
4With 4mol NH
4NO
3Be dissolved in the distilled water and form homogeneous mixture solotion and join in the polytetrafluoroethylene hydrothermal reaction kettle, at 150 ℃ of lower isothermal reaction 6h, naturally cool to again room temperature, fully wash through deionized water and absolute ethyl alcohol, 90 ℃ of lower heating, drying 11h get nano material of manganese dioxide.
Preparation LiMn
1.8
Ti
0.2
O
4
Particle
With above-mentioned nano material of manganese dioxide, titanium oxide and lithium carbonate Li in molar ratio
:Mn
:Ti=1
:1.8
:0.2, adopt ball-milling method to mix after, with 1100 ℃ temperature sintering 1 hour under argon gas atmosphere, then broken, classification obtains LiMn
1.8Ti
0.2O
4Particle.
Coat zirconia
With described LiMn
1.8Ti
0.2O
4Particle, melting agent boron hydroxide and zirconia are according to mol ratio 1
:0.3
:0.08 mix, join in the middle of the fusion device, fusion temperature is 700 ℃, adjusting rotary speed is 6500rpm, and time of fusion is 2h, puts into Muffle furnace after the taking-up, the temperature that Muffle furnace is set is 1000 ℃, and constant temperature 6h is cooled to room temperature acquisition surface and is coated with zirconic modified lithium manganate cathode material.
Comparative example
With 230.1g Li
2CO
3, 691.6g MnO
2, 78.3g Co (CH
3COO)
24H
2The O pressed powder adds in the beaker, and adding concentration is the H of 15wt%
2O
2The aqueous solution, 50 ℃ are constantly stirred, behind the about 12h of reaction, filter.After Washing of Filter Cake, drying, add in the ball grinder with the 500ml absolute ethyl alcohol, the mass ratio of Φ 10 stainless steel balls and above-mentioned raw materials is 0.55, planetary ball mill rotating speed 150r/min carries out ball milling 1h.With the insulation calcining 12h after oxygen content is that 5 ℃/min rises to 650 ℃ in 30% the atmosphere of the mixture behind the above-mentioned ball milling, obtain 750g end-product doping type lithium manganate pressed powder.
With embodiment one, two and comparative example gained anode composite material of lithium ion battery, be dissolved in the 1-METHYLPYRROLIDONE (NMP) by 50mg/mL with 80: 10: 10 mass ratioes with acetylene black (conductive agent), Kynoar (binding agent PVDF) respectively, magnetic agitation is even, then paste is coated on the nickel foam and drying, strike out the pole piece of 1cm * 1cm, be assembled into battery at 1M LiPF
6/ (EC+DMC (volume ratio is 1: 1)) organic system electrolyte.Be to carry out electric performance test under 45 ℃ at probe temperature, after tested this embodiment one with two material compare with the material of comparative example, first discharge specific capacity has promoted more than the 50-60%, cycle life has improved more than 2.
Claims (4)
1. the preparation method of a lithium ion battery usefulness modified lithium manganate cathode material is characterized in that, comprises the steps:
Step 1, the preparation in manganese source
Get 2-4mol KMnO
4Be dissolved into the 2-4mol ammonium salt and form homogeneous mixture solotion in the distilled water, at 120-150 ℃ of lower isothermal reaction 6-10h, be cooled to again room temperature, collecting precipitation, through deionized water and absolute ethanol washing, drying gets nano material of manganese dioxide;
Step 2, preparation LiMn
2-xTi
xO
4Particle
With above-mentioned nano material of manganese dioxide, titanium oxide and lithium carbonate Li in molar ratio
:Mn
:Ti=1
:(2-x)
:(x), adopt ball-milling method to mix after, then broken with 900 ℃-1100 ℃ temperature under argon gas atmosphere sintering 10-20 hour, obtain LiMn
2-xTi
xO
4Particle, wherein 0.1≤x≤0.2;
Step 3 coats zirconia
With described LiMn
2-xTi
xO
4Particle, melting agent boron hydroxide and zirconia are according to mol ratio 1
:(0.2-0.3)
:(0.06-0.08) mix, join in the middle of the fusion device, fusion temperature is 500-700 ℃, and adjusting rotary speed is 6000-6500rpm, and time of fusion is 2-3h; Taking-up is placed under 900-1000 ℃, and constant temperature 6-8h is cooled to room temperature acquisition surface and is coated with zirconic modified lithium manganate cathode material.
2. method according to claim 1 is characterized in that, drying condition described in the step 1 is: 70-90 ℃ of lower heating, drying 11-13h.
3. method according to claim 1 is characterized in that, ammonium salt is selected from NH described in the step 1
4NO
3, NH
4Cl.
4. lithium ion battery modified lithium manganate cathode material of method preparation as claimed in claim 1.
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|---|---|---|---|
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|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108336331A (en) * | 2017-01-17 | 2018-07-27 | 三星电子株式会社 | Electrode active material, the lithium secondary battery comprising the electrode active material and the method for preparing the electrode active material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005285720A (en) * | 2004-03-31 | 2005-10-13 | Sanyo Electric Co Ltd | Non-aqueous electrolyte secondary battery |
| CN102280617A (en) * | 2011-07-06 | 2011-12-14 | 中国科学院过程工程研究所 | Carbon material modified composite lithium manganese oxide cathode material applied to lithium ion battery and preparation method thereof |
| CN102420331A (en) * | 2011-10-25 | 2012-04-18 | 中国海洋石油总公司 | Coating modification method of lithium manganate |
| CN102569807A (en) * | 2011-11-10 | 2012-07-11 | 中国科学院宁波材料技术与工程研究所 | Coated-modified lithium manganese positive electrode material and preparation method thereof |
-
2012
- 2012-10-17 CN CN2012103934269A patent/CN102916173A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005285720A (en) * | 2004-03-31 | 2005-10-13 | Sanyo Electric Co Ltd | Non-aqueous electrolyte secondary battery |
| CN102280617A (en) * | 2011-07-06 | 2011-12-14 | 中国科学院过程工程研究所 | Carbon material modified composite lithium manganese oxide cathode material applied to lithium ion battery and preparation method thereof |
| CN102420331A (en) * | 2011-10-25 | 2012-04-18 | 中国海洋石油总公司 | Coating modification method of lithium manganate |
| CN102569807A (en) * | 2011-11-10 | 2012-07-11 | 中国科学院宁波材料技术与工程研究所 | Coated-modified lithium manganese positive electrode material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108336331A (en) * | 2017-01-17 | 2018-07-27 | 三星电子株式会社 | Electrode active material, the lithium secondary battery comprising the electrode active material and the method for preparing the electrode active material |
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Application publication date: 20130206 |
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