CN102856544A - Preparation method of nano nickel lithium manganate - Google Patents
Preparation method of nano nickel lithium manganate Download PDFInfo
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- CN102856544A CN102856544A CN2012103864035A CN201210386403A CN102856544A CN 102856544 A CN102856544 A CN 102856544A CN 2012103864035 A CN2012103864035 A CN 2012103864035A CN 201210386403 A CN201210386403 A CN 201210386403A CN 102856544 A CN102856544 A CN 102856544A
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Abstract
The invention discloses a preparation method of nano nickel lithium manganate. The method comprises the following steps of: (1) dissolving lithium salt, manganese salt and nickel salt, which a soluble in alcohol compounds, in a solvent containing the alcohol compounds according to the mole ratio of 2:3:1 to obtain the mixed solution containing the lithium salt, the manganese salt and the nickel salt; (2) adding acetic acid or ammonium acetate in the mixed solution of the salts prepared in the step (1); (3) adding ammonia or ammonia water into the mixed solution of the salts prepared in the step (2) to obtain a solution containing milk-white sediment; (4) while heating and stirring, introducing oxygen or air into the solution containing milk-white sediment obtained in the step (3), until obtaining the steady black solution, continuing to heat, until obtaining the black substance; (5) directly adding the substance in a high temperature furnace, heating up to 600-850 degrees centigrade, preserving heat for 19 hours, and finally obtaining the nano particles of LiNio.5Mn1.5O4.
Description
Technical field
[0001] the present invention relates to the preparation method of nickel LiMn2O4 nano particle.
Background technology
[0002] lithium ion battery has superior chemical property and good environmental friendliness performance, be widely used in the key areas such as mobile communication, laptop computer, electric tool as power supply, and be subject to increasing attention in electrokinetic cell fields such as electric automobiles.Positive electrode is the important component part of lithium ion battery.5V high-voltage spinel structure positive electrode LiNi
0.5Mn
1.5O
4, with its high specific capacity, specific power, operating voltage (about 4.7V) and lower material cost, become one of positive electrode that field of batteries receives much concern.Yet the high rate performance of this material is not ideal, by material nanoization can be addressed this problem.The size of nano anode material is little, Li
+It is short that the path is taken off in embedding, can discharge better the stress of doff lithium, accelerates Li
+Diffusion improves the fast charging and discharging ability; The surface tension of nano anode material is larger than common positive electrode, and in the embedding lithium process, solvent molecule is difficult to enter the lattice of material, therefore can stop the common embedding of solvent molecule, the cycle life that prolongs battery; The specific area of nano anode material is larger, and is large with the contact area of electrolyte, and more Li can be provided
+The embedding dislocation is put; The high porosity on nano anode material surface also makes embedding lithium room increase, and has the capacity higher than common positive electrode.
The preparation nanoscale LiNi that reports in the existing document
0.5Mn
1.5O
4Method high polymer method, profit Xiang Fa etc. are arranged.Such as Lifen Xiao, Yanqiang Zhao, Yanyan Yang etc., utilize lithium nickel manganese salt to be dissolved in the acrylic acid solution, then add initiator ammonium persulfate, cause acrylic acid generation polymerization and obtain polyacrylate, then order has obtained the spinel-type LiNi about 100 nm at 120 ℃, 450 ℃, 600 ~ 900 ℃ lower heating 12 h, 6 h, 3 h
0.5Mn
1.5O
4Particle (Lifen Xiao, Yanqiang Zhao, Yanyan Yang, Xinping Ai, Hanxi Yang and Yuliang Cao .Electrochemical properties of nano-crystalline LiNi0.5Mn1.5O4 synthesized by polymer-pyrolysis method [J]. J Solid State Electrochem, 2008,12:687-691).This preparation method, the use of acrylic acid and ammonium persulfate has greatly increased preparation cost, and the use of ammonium persulfate and polyacrylic burning process, has seriously increased the pollution level of preparation technology to environment.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of nano nickel LiMn2O4.
The present invention is a kind of nano nickel LiMn2O4The preparation method, the steps include:
Lithium salts, manganese salt, the nickel salt that (1) will dissolve in alcohol compound are dissolved in the solvent that contains alcohol compound for the amount of 2:3:1 in molar ratio, obtain containing the mixed solution of lithium salts, manganese salt and nickel salt;
(2) acetic acid or ammonium acetate are added in the mixed solution of the salt of preparing in the step (1);
(3) ammonia or ammoniacal liquor are added in the mixed solution of step (2) gained salt, obtain containing milky white precipitate solution;
(4) when adding thermal agitation, gained contains in the solution of milky white precipitate and passes into oxygen or air in the step (3), until obtain the solution of stable black, continues heating, until obtain atrament;
(5) above-mentioned substance is directly placed high temperature furnace be warming up to 600 ℃ ~ 850 ℃ lower maintenances 1 ~ 19 hour, can obtain LiNi
0.5Mn
1.5O
4Nano particle.
The present invention has at first made the value Mn material, utilizes material and the value Mn unstable character that decomposition can occur under hot conditions, has obtained Uniform Dispersion, the LiNi that particle is little
0.5Mn
1.5O
4Presoma, and directly obtained the oxide of value Mn by the decomposition of value Mn material, thereby do not need extra high temperature to allow again the manganese of lower valency be oxidized to high valence state, thereby need not the step that material at first carries out oxidation Decomposition at low temperatures, greatly shorten the reaction time, finally obtained finely disseminated nano level spinel structure 5 V high voltage material LiNi by method simply
0.5Mn
1.5O
4
The LiNi that the present invention and document have been reported
0.5Mn
1.5O
4The preparation method of nano particle compares, because the introducing of value Mn compound in presoma, so that need not the low-temperature oxidation step in the preparation process, can directly under sintering temperature, make well-crystallized's nano particle, so that (total preparation time is lower than 20 h) with short production cycle, technological process is simpler, can carry out low temperature and synthesize.
Description of drawings
Fig. 1 is the XRD spectra of case study on implementation 1 products therefrom; Fig. 2 is case study on implementation 1 products obtained therefrom high power Electronic Speculum figure.
Embodiment
The present invention is a kind of nano nickel LiMn2O4The preparation method,
The nickel LiMn2O4 namelyLiNi
0.5Mn
1.5O
4, the steps include:
Lithium salts, manganese salt, the nickel salt that (1) will dissolve in alcohol compound are dissolved in the solvent that contains alcohol compound for the amount of 2:3:1 in molar ratio, obtain containing the mixed solution of lithium salts, manganese salt and nickel salt;
(2) acetic acid or ammonium acetate are added in the mixed solution of the salt of preparing in the step (1);
(3) ammonia or ammoniacal liquor are added in the mixed solution of step (2) gained salt, obtain containing milky white precipitate solution;
(4) when adding thermal agitation, gained contains in the solution of milky white precipitate and passes into oxygen or air in the step (3), until obtain the solution of stable black, continues heating, until obtain atrament;
(5) above-mentioned substance is directly placed high temperature furnace be warming up to 600 ℃ ~ 850 ℃ lower maintenances 1 ~ 19 hour, can obtain LiNi
0.5Mn
1.5O
4Nano particle.
According to above-described
The nano nickel LiMn2O4The preparation method, the lithium salts that dissolves in alcohol compound described in the step (1) is one or more the mixture in lithium nitrate, lithium acetate, lithium sulfate and the lithium chloride, manganese salt can be one or more the mixture in manganese acetate, manganese chloride, manganese nitrate and the manganese sulfate, and nickel salt can be one or more the mixture in nickel nitrate, nickelous sulfate, nickel acetate and the nickel chloride.
According to the preparation method of above-described nano nickel LiMn2O4, the alcohols solvent described in the step (1) can be one or more the mixture in methyl alcohol, ethanol, propyl alcohol and the butanols, and wherein the mass fraction of alcohols material can be 90% ~ 99.9%.
According to the preparation method of above-described nano nickel LiMn2O4, the acetic acid that adds in the step (2) or the mole of ammonium acetate are 0.15 times ~ 15 times of lithium salts mole.
According to the preparation method of above-described nano nickel LiMn2O4, in the step (3) add ammonia or ammoniacal liquor, its mole is 0.15 times ~ 15 times of lithium salts mole.
According to the preparation method of above-described nano nickel LiMn2O4, the heating-up temperature described in the step (4) can be 60 ℃ ~ 120 ℃, and agitating mode is mechanical agitation, or magnetic agitation.
According to the preparation method of above-described nano nickel LiMn2O4, required in the step (4) to pass into mole total amount oxygenous in the gas be 0.1 times ~ 30 times of manganese salt mole.
Preparation method according to above-described nano nickel LiMn2O4, the concrete operation method of step (4) is to stir in air first or pass into air or pass into oxygen under stirring condition, until after obtaining stable dark solution, under stirring condition, heat again, until obtain atrament.
Below by embodiment the present invention is described in further detail, following execution mode is descriptive, is not determinate, can not limit protection scope of the present invention with this.
Embodiment 1: get 0.01 mol lithium nitrate, 0.015 mol four water manganese acetates, 0.005 mol six water nickel nitrates, be dissolved in 75 mL mass ratioes and be in the beaker of ethanol/water solution of 99.9:0.1 and heat, add 15 mL mass fractions and be 24% concentrated ammonia liquor, obtain containing the solution of milky white precipitate, then beaker is transferred in the oil bath pan, regulating temperature is 85 ℃, and carries out mechanical agitation, and the solution colour that contains milky white precipitate slowly becomes aterrimus, behind about 10 min, form stable dark solution, after continuing to heat about 10 min, can obtain atrament.This atrament is placed in the Muffle furnace, keeps 15 h at 750 ℃, can obtain the nanoscale LiNi of spinel structure
0.5Mn
1.5O
4Product.About 16 h of total time spent of preparation process.Products obtained therefrom product XRD schemes as shown in Figure 1, and high power Electronic Speculum figure as shown in Figure 2.
Embodiment 2: get 0.01 mol lithium nitrate, 0.015mol four water manganese acetates, 0.005 mol six water nickel nitrates, 0.01mol ammonium acetate, be dissolved in 75 mL mass ratioes and be in the beaker of ethanol/water solution of 95:5, add the 15mL mass fraction and be 24% concentrated ammonia liquor, obtain containing the solution of milky white precipitate, and with magnetic agitation, obtain the solution of black behind about 15 min.The beaker that fills dark solution is put into the oil bath pan heating and carried out magnetic agitation, and regulating temperature is 95 ℃, after continuing to heat about 25 min, can obtain atrament.This atrament is placed in the Muffle furnace, keeps 12 h at 800 ℃, can obtain the nanoscale LiNi of spinel structure
0.5Mn
1.5O
4Product.Total about 13 h of time spent.
Embodiment 3: get the 0.02mol lithium nitrate, 0.03mol four water manganese acetates, 0.01 mol six water nickel nitrates, 0.02mol ammonium acetate, be dissolved in 100 mL mass ratioes and be in the beaker of ethanol/water solution of 90:10, add 20 mL mass fractions and be 24% concentrated ammonia liquor, obtain containing the solution of milky white precipitate, then beaker is transferred in the oil bath pan and heats, regulating temperature is 85 ℃, and carry out mechanical agitation, the solution colour that contains milky white precipitate slowly becomes aterrimus, behind about 15min, forms stable dark solution, after continuing the about 20min of heating, can obtain atrament.This atrament is placed in the Muffle furnace, keeps 10 h at 850 ℃, can obtain the nanoscale LiNi of spinel structure
0.5Mn
1.5O
4Product.About 11 h of total time spent of preparation process.
Claims (8)
1. the preparation method of a nano nickel LiMn2O4 the steps include:
Lithium salts, manganese salt, the nickel salt that (1) will dissolve in alcohol compound are dissolved in the solvent that contains alcohol compound for the amount of 2:3:1 in molar ratio, obtain containing the mixed solution of lithium salts, manganese salt and nickel salt;
(2) acetic acid or ammonium acetate are added in the mixed solution of the salt of preparing in the step (1);
(3) ammonia or ammoniacal liquor are added in the mixed solution of step (2) gained salt, obtain containing milky white precipitate solution;
(4) when adding thermal agitation, gained contains in the solution of milky white precipitate and passes into oxygen or air in the step (3), until obtain the solution of stable black, continues heating, until obtain atrament;
(5) above-mentioned substance is directly placed high temperature furnace be warming up to 600 ℃ ~ 850 ℃ lower maintenances 1 ~ 19 hour, can obtain the nano particle of nano nickel LiMn2O4.
2. the preparation method of described nano nickel LiMn2O4 according to claim 1, it is characterized in that, the lithium salts that dissolves in alcohol compound described in the step (1) is one or more the mixture in lithium nitrate, lithium acetate, lithium sulfate and the lithium chloride, manganese salt can be one or more the mixture in manganese acetate, manganese chloride, manganese nitrate and the manganese sulfate, and nickel salt can be one or more the mixture in nickel nitrate, nickelous sulfate, nickel acetate and the nickel chloride.
3. the preparation method of described nano nickel LiMn2O4 according to claim 1, it is characterized in that, alcohols solvent described in the step (1) can be one or more the mixture in methyl alcohol, ethanol, propyl alcohol and the butanols, and wherein the mass fraction of alcohols material can be 90% ~ 99.9%.
4. the preparation method of described nano nickel LiMn2O4 according to claim 1 is characterized in that the acetic acid that adds in the step (2) or the mole of ammonium acetate are 0.15 times ~ 15 times of lithium salts mole.
5. the preparation method of described nano nickel LiMn2O4 according to claim 1 is characterized in that, in the step (3) add ammonia or ammoniacal liquor, its mole is 0.15 times ~ 15 times of lithium salts mole.
6. the preparation method of described nano nickel LiMn2O4 according to claim 1 is characterized in that the heating-up temperature described in the step (4) can be 60 ℃ ~ 120 ℃, and agitating mode is mechanical agitation, or magnetic agitation.
7. the preparation method of described nano nickel LiMn2O4 according to claim 1 is characterized in that, required in the step (4) to pass into mole total amount oxygenous in the gas be 0.1 times ~ 30 times of manganese salt mole.
8. the preparation method of described nano nickel LiMn2O4 according to claim 1, it is characterized in that, the concrete operation method of step (4) is to stir in air first or pass into air or pass into oxygen under stirring condition, until after obtaining stable dark solution, under stirring condition, heat again, until obtain atrament.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103227314A (en) * | 2013-04-17 | 2013-07-31 | 嘉峪关大友嘉能化工有限公司 | Preparation method of ternary cathode material |
| CN103227315A (en) * | 2013-04-17 | 2013-07-31 | 嘉峪关大友嘉能化工有限公司 | Preparation method of battery positive electrode material LiMn2O4 |
| JP2016524576A (en) * | 2013-03-15 | 2016-08-18 | ナノ ワン マテリアルズ コーポレーション | Complexation precursor formulation methodology for industrial production of fine and ultrafine powders of lithium metal oxides and nanopowder for battery applications |
| CN108023087A (en) * | 2017-12-01 | 2018-05-11 | 洛阳师范学院 | A kind of SiO2The preparation method of the nickel lithium manganate cathode material of cladding |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016524576A (en) * | 2013-03-15 | 2016-08-18 | ナノ ワン マテリアルズ コーポレーション | Complexation precursor formulation methodology for industrial production of fine and ultrafine powders of lithium metal oxides and nanopowder for battery applications |
| CN103227314A (en) * | 2013-04-17 | 2013-07-31 | 嘉峪关大友嘉能化工有限公司 | Preparation method of ternary cathode material |
| CN103227315A (en) * | 2013-04-17 | 2013-07-31 | 嘉峪关大友嘉能化工有限公司 | Preparation method of battery positive electrode material LiMn2O4 |
| CN103227314B (en) * | 2013-04-17 | 2015-05-13 | 嘉峪关大友嘉能化工有限公司 | Preparation method of ternary cathode material |
| CN103227315B (en) * | 2013-04-17 | 2015-05-13 | 嘉峪关大友嘉能化工有限公司 | Preparation method of battery positive electrode material LiMn2O4 |
| CN108023087A (en) * | 2017-12-01 | 2018-05-11 | 洛阳师范学院 | A kind of SiO2The preparation method of the nickel lithium manganate cathode material of cladding |
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