CN102664259A - Method for preparing cathode material of lithium ion battery - Google Patents
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- CN102664259A CN102664259A CN2012101341199A CN201210134119A CN102664259A CN 102664259 A CN102664259 A CN 102664259A CN 2012101341199 A CN2012101341199 A CN 2012101341199A CN 201210134119 A CN201210134119 A CN 201210134119A CN 102664259 A CN102664259 A CN 102664259A
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Abstract
The invention provides a method for preparing a cathode material of a lithium ion battery. The method comprises the following steps of: a) dispersing a lithium source compound, a manganese source compound, a phosphorus source compound and a carbon source compound in a solvent, and thus obtaining mixed slurry; b) curing the slurry which is obtained in the step a); and c) calcinating the cured slurry which is obtained in the step b), and thus obtaining the cathode material of the lithium ion battery. The method provided by the invention is easy to operate and has mild conditions, and the prepared cathode material is high in charge and discharge capacity and high in magnification characteristic.
Description
Technical field
The present invention relates to the electrode material preparation field, be specifically related to a kind of preparation method of anode material for lithium-ion batteries.
Background technology
Research shows, this obviously is superior to traditional layer structure material (cobalt acid lithium, lithium nickelate and ternary material), its representative materials LiFePO4 (LiFePO on aspect two to the phosphate system material of olivine-type structure in security performance and cycle life
4) confirmed by academia and industrial circle broad research, and be widely used in fields such as electrokinetic cell and energy-storage battery.But the voltage platform of lithium metal 3.4V defines the lifting of LiFePO4 energy density relatively, thereby influences the market competitiveness of this material.Yet lithium manganese phosphate (LiMnPO
4) material and LiFePO4 (LiFePO
4) compare, can current potential be improved 0.7V, also have the theoretical specific capacity of 171mAh/g, therefore be expected to become a new generation the high energy density lithium ion battery positive electrode and get most of the attention.But the electronic conductivity of lithium manganese phosphate material and lithium ion diffusion rate are lower than LiFePO4, so the lithium manganese phosphate material of non-modified can't satisfy the practical application needs at all.
At present, people adopt carbon to coat, and doped with metal elements and material granule nanometerization improve the electronic conductivity and the evolving path that shortens lithium ion of material, thereby improve the chemical property of lithium manganese phosphate material.At document Electrochimica Acta, 2011,56 (11): among the 40520-4057, people such as Huihua Yi are with the LiH of stoichiometric proportion
2PO
4, MnC
4H
6O
44H
2O, FeC
2O
42H
2O, MgC
4H
6O
44H
2O, H
2C
2O
42H
2O and 14wt.% sucrose mix abundant ball milling 6h, and under the argon gas atmosphere protection, 800 ℃ of high-temperature calcination 10h get LiMn then
0.9Fe
0.05Mg
0.05PO
4/ C material, the discharge capacity first that gets 0.1C through electrochemical property test is 140mAh/g.Though this solid phase method technology is simple, suitability for industrialized production is convenient, and it is big that the prepared material of this method still exists particle, and particle diameter heterogeneity and carbon coat problems such as imperfect, and this will have a strong impact on the cycle performance of material, performances such as high rate performance and high low temperature.In document Journal of Power Sources, 2007,174 (2): among the 949-953; People such as Thierry Drezen come the control material grain diameter through adopting sol-gal process and regulation and control sintering temperature; With lithium acetate, manganese acetate and ammonium dihydrogen phosphate are dissolved in the deionized water, add the chelating agent glycolic then earlier; Between 60-75 ℃, obtain gel, then calcine 3h down and get LiMnPO in different temperature (400-800 ℃)
4Material.Characterize to such an extent that 520 ℃ of material particle size minimums of calcining preparation are 140nm through ESEM, its 0.1C discharge capacity first is 116mAh/g.Though collosol and gel can make reactant that intermolecular mixing and reaction take place; But its complex process; Be difficult to large-scale production; And low-temperature bake is handled material can reduce the crystallinity of material, thereby causes material structure bad stability and chemical property rapid deterioration, is not fit to the production application needs.
Summary of the invention
The technical problem that the present invention will solve is to provide a kind of preparation method of anode material for lithium-ion batteries, and this method is easy to operate, mild condition, and the positive electrode charge/discharge capacity of preparation is high, and multiplying power property is high.
In order to solve above technical problem, the invention provides a kind of preparation method of anode material for lithium-ion batteries, comprising:
A) Li source compound, manganese source compound, P source compound and carbon-source cpd are scattered in the solvent, obtain mixed slurry;
B) slurry that step a) is obtained carries out the slaking operation;
C) the slurry calcining after the slaking that step b) is obtained obtains anode material for lithium-ion batteries.
Preferably, said Li source compound, manganese source compound, P source compound are 0.90～1.20: 1.00～0.80: 1～1.10 in molar ratio.
Preferably, said carbon-source cpd accounts for the 10wt%～30wt% of Li source compound, manganese source compound, P source compound quality comprehensive.
Preferably, said Li source compound is lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate, lithium phosphate, lithium dihydrogen phosphate or phosphoric acid hydrogen two lithiums.
Preferably, said manganese source compound is manganese acetate, manganese sulfate, manganese oxalate, manganese nitrate, manganese dioxide, mangano-manganic oxide, manganese sesquioxide managnic oxide or manganous hydroxide.
Preferably, said P source compound is ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid, lithium phosphate, lithium dihydrogen phosphate or phosphoric acid hydrogen two lithiums.
Preferably, said carbon-source cpd is conductive black, CNT, acetylene black, Graphene, lactose, sucrose, ascorbic acid, phenolic resins, polyvinyl alcohol, glucose or polysaccharide.
Preferably, the operation of the slaking in the said step b) is specially:
Mixed slurry under 30～80 ℃, is stirred 2～24h.
Preferably, the speed of said stirring is 20～100r/min.
Preferably, also be included in the said mixed slurry and add doped metallic elements.
The invention provides a kind of preparation method of anode material for lithium-ion batteries, comprise, a) Li source compound, manganese source compound, P source compound and carbon-source cpd are scattered in the solvent, obtain mixed slurry; B) slurry that step a) is obtained carries out the slaking operation; C) the slurry calcining after the slaking that step b) is obtained obtains anode material for lithium-ion batteries.Preparation method provided by the invention increases the slaking operation on the basis of existing solid phase method, let mixed slurry under the temperature of setting, be uniformly dispersed, and the reaction at beginning initial stage; Owing to disperse more even; Physical mixed and chemical reaction between the atom are carried out simultaneously, make the anode material for lithium-ion batteries particle diameter of preparation less and even, make the preparation process more controlled; The sol-gal process of comparing; Simplified production stage, reduced requirement, improved production efficiency and reduced production cost working condition.
Description of drawings
The XRD spectra of Fig. 1 embodiment of the invention 1 spray drying afterproduct (a) and comparative example 1 spray drying afterproduct (b);
The SEM spectrogram of the lithium manganese phosphate material of Fig. 2 embodiment of the invention 1 preparation;
The SEM spectrogram of the lithium manganese phosphate material of Fig. 3 comparative example 1 preparation of the present invention;
The CR2032 button half-cell of the lithium manganese phosphate material preparation of Fig. 4 the inventive method preparation is in room temperature, the 1C discharge curve in 2.0～4.5V voltage range;
The CR2032 button half-cell of the lithium manganese phosphate material preparation of Fig. 5 the inventive method preparation is in room temperature, the 1C electrochemistry cycle performance curve in 2.0～4.5V charging/discharging voltage scope.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiments of the invention are described, but should be appreciated that these just restriction for further specifying feature and advantage of the present invention rather than patent of the present invention being required is described.
The invention provides a kind of preparation method of anode material for lithium-ion batteries, comprising:
A) Li source compound, manganese source compound, P source compound and carbon-source cpd are scattered in the solvent, obtain mixed slurry; B) slurry that step a) is obtained carries out the slaking operation; C) the slurry calcining after the slaking that step b) is obtained obtains anode material for lithium-ion batteries.
Preparation method provided by the invention a kind ofly prepares the improvement of carrying out on the anode material for lithium-ion batteries basis at existing solid phase method; The compound that the method that existing solid phase method prepares anode material for lithium-ion batteries will have required element mixes; Through coprecipitation, under the effect of precipitation reagent, form the compound acid salt deposition of metallic element then, and then it is calcined or roasting; Obtain the composite oxides of metallic element; Though this method is quick, the particle diameter of the positive electrode of preparation is inhomogeneous, causes the electric property defective of positive electrode.
The present invention uses the slaking operation as the process of reacting between Li source compound, manganese source compound, P source compound and the carbon-source cpd in order to solve the problems of the technologies described above.So-called slaking is meant in certain temperature, the time with stir speed down, let reactant precursor slurry in agitated reactor, carry out id reaction, eliminate out-phase.The applicant finds in maturing process; Anion such as metal cation in the mixed slurry and phosphate radical slowly form granular precursor through physical mixed and chemical reaction; This grain diameter little many of the grain diameter of coprecipitation preparation that compare; And it is evenly, so said granular precursor is more even through the also littler open country of positive electrode particle diameter that obtains after calcining.Increased maturation stage in sum; Can solving existing conventional solid phase method, to prepare the existing particle of lithium manganese phosphate positive electrode big; Particle diameter heterogeneity and particle surface carbon coat incomplete problem, thereby improve cycle performance, high rate performance and the high temperature performance of material.It is specific as follows that a kind of curing process prepares the method for lithium manganese phosphate positive electrode:
Get Li source compound, manganese source compound, P source compound, its molar ratio is 0.90～1.20: 1.00～0.80: 1～1.10, add carbon-source cpd then, and be dispersed in the solvent, obtain mixed slurry.Said solvent is preferably water, more preferably deionized water.Said carbon-source cpd quality is the 1Owt%～30wt% of Li source compound, manganese source compound, P source compound quality comprehensive.According to the present invention, the solid content of various source compounds is comprehensive for being preferably 20wt%～50wt% in the said mixed slurry, more preferably 30wt%～40wt%.
According to the present invention, said Li source compound is preferably lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate, lithium phosphate, lithium dihydrogen phosphate or phosphoric acid hydrogen two lithiums.Said manganese source compound is preferably manganese acetate, manganese sulfate, manganese oxalate, manganese nitrate, manganese dioxide, mangano-manganic oxide, manganese sesquioxide managnic oxide or manganous hydroxide.Said P source compound is preferably ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid, lithium phosphate, lithium dihydrogen phosphate or phosphoric acid hydrogen two lithiums.Said carbon-source cpd is preferably conductive black, CNT, acetylene black, lactose, sucrose, ascorbic acid, phenolic resins, polyvinyl alcohol, glucose or polysaccharide.
According to the present invention, for the electric conductivity and the specific capacity of the positive electrode that improves preparation, the present invention is selected in addition in the said mixed slurry and adds doped metallic elements; Said doped metallic elements is preferably has metallic element and the thulium that good charge shifts transfer ability, Ti more preferably, Co; Fe, Mg, V; Al, one or more among Cr and the Nb.Said doped metallic elements and Li source compound are preferably 0～0.20: 0.90～1.20 in molar ratio.Said doped metallic elements adds in the said mixed slurry with the formation of slaine or metal oxide.Be preferably carbonate, phosphate, halide or the oxide of said doped metallic elements, more preferably titanium dioxide, ferric carbonate, aluminium oxide, magnesia, vanadic oxide most preferably are ferric carbonate, aluminium oxide or magnesia.
More even for raw material is disperseed, the also preferred ball-milling method that uses of the present invention carries out the ball milling operation to said mixed slurry, and the said ball milling time is 5～15h.The ball milling disposed slurry is carried out the slaking operation.The slaking operation is preferably carried out in the container with heating and agitating function.Curing temperature is preferably 20～80 ℃, more preferably 30～70 ℃, most preferably is 40～60 ℃; Curing time is preferably 6～24h, and more preferably 10～18h most preferably is 12～15h; The mixing speed of stirring motor is preferably 20～100r/min during slaking, more preferably 30～80r/min, more preferably 40～60r/min; More thorough for what calcining was carried out, according to the present invention, because slaking is that mixed slurry is fully disperseed and initial reaction, so that curing temperature is difficult for is too high, in order to avoid solvent evaporation is too fast.Because the solvent that the present invention uses is a water; So solvent evaporation causes the mixed slurry jitter time not enough after being higher than 80 ℃; Disperse inhomogeneous; Reaction time shortens, and makes the particle diameter of granular precursor thick, and the positive electrode of final preparation can't reach the desired performance index of preparation method provided by the invention.
The present invention preferably carries out drying process with the slurry after the said slaking; The drying means that the mode of said drying is known for those skilled in the art; Methods such as spray drying, air dry, oven dry for example, the slurry after the present invention more preferably uses spray drying process to said slaking carries out drying.Owing to formed the part granular precursor in the slurry after slaking this moment, so spray drying can not influence the particle diameter of granular precursor.
After said mixed slurry drying, the presoma that obtains is preferably calcined under the nitrogen atmosphere protection, and said calcining heat is preferably 600 ℃～800 ℃, more preferably 650 ℃～750 ℃; Calcination time is preferably 2～16h, and more preferably 5～12h most preferably is 8～10h.At last calcined product is pulverized and 300 orders that sieve get product lithium manganese phosphate positive electrode.
Implementation result of the present invention and advantage thereof are: in the solid phase method of routine, increase curing process; Can make the precursor slurry carry out intermolecular more completely reaction, eliminate out-phase, it is big to have solved material granule; The incomplete problem of particle diameter heterogeneity and carbon coating layer; Improve material electronics conductivity and lithium ion diffusion rate, thereby improved cycle performance, high rate performance and the high temperature performance of lithium manganese phosphate material.
In order further to set forth scheme of the present invention, below be the specific embodiment of the invention.
Embodiment 1:
Take by weighing the 41.96g lithium hydroxide earlier, the 91.96g manganese carbonate, the 115.03g ammonium dihydrogen phosphate, 10.6g ferric carbonate and 25.95g sucrose, and above-mentioned raw materials is scattered in the deionized water of 1.3L; Carry out abundant ball milling then, the ball milling time is 5h, then the ball milling disposed slurry is transferred to and is carried out slaking (slaking principle: MnCO in the electric heating stirred autoclave
3+ NH
4H
2PO
4→ NH
4MnPO
4+ H
2O+CO
2NH
4MnPO
4+ LiOH → LiMnPO
4+ NH
3+ H
2O), curing temperature is controlled at 80 ℃, and the curing time is 6h, and mixing speed is 100r/min; After treating that slaking finishes, slurry is carried out spray drying, under the nitrogen atmosphere protection, carry out high-temperature calcination then, calcining heat is 600 ℃, and calcination time is 16h, at last calcined product is pulverized and 300 orders that sieve get the product anode material for lithium-ion batteries.
Comparative example 1:
Take by weighing the 41.96g lithium hydroxide earlier, the 91.96g manganese carbonate, the 115.03g ammonium dihydrogen phosphate, 10.6g ferric carbonate and 25.95g sucrose, and above-mentioned raw materials is scattered in the deionized water of 1.3L; Carry out abundant ball milling then, the ball milling time is 5h, then slurry is carried out spray drying; Under the nitrogen atmosphere protection, carry out high-temperature calcination then; Calcining heat is 600 ℃, and calcination time is 16h, at last calcined product is pulverized and 300 orders that sieve get the product anode material for lithium-ion batteries.
Adopt day island proper Tianjin XRD-6000 type x-ray powder diffraction instrument (XRD) that embodiment 1 spray drying afterproduct (a) and comparative example 1 spray drying afterproduct (b) are characterized, the result is as shown in Figure 1, and the XRD diffraction maximum among Fig. 1 (a) is respectively NH
4MnPO
4Index peak (◆) and LiMnPO
4Index peak (●), and the XRD diffraction maximum among Fig. 1 (b) remains the index peak of raw material reaction thing, this has shown that curing process can make the reactant slurry carry out self intermolecular reaction, thereby generates NH
4MnPO
4And LiMnPO
4Presoma.Adopt the S-4800 of HIT type field emission scanning electron microscope (SEM) that embodiment 1 is characterized with comparative example 1 product lithium manganese phosphate; The result as shown in Figures 2 and 3; Shown that curing process can make the reactant slurry carry out self intermolecular reaction; Thereby make material granule little, uniform particle diameter and carbon coating layer are complete.Embodiment 1 is mixed by 90: 5: 5 mass ratioes with acetylene black conductive agent and Kynoar binding agent respectively with comparative example 1 product anode material for lithium-ion batteries; Be applied on the aluminum foil current collector; Use sheet-punching machine to make the electrode slice of diameter after 80 ℃ of oven dry as 1cm; Negative pole is a metal lithium sheet, and barrier film is Celgard 2400, and electrolyte solution is EC+DMC+EMC+1mol/LLiPF
6, at the German Braun UNlab of company type inert atmosphere glove box (O
2And H
2The content of O is all less than 1ppm) in be assembled into CR2032 button half-cell.Adopt the blue electric CT2001A type battery test system in Wuhan that CR2032 button half-cell is carried out electrochemical property test, voltage range is 2.0～4.5V, and current density converts by 1C=170mA/g, and test result is seen Fig. 4 and Fig. 5.Fig. 4 show the prepared lithium manganese phosphate material 1C of the solid phase method that increased the curing process step first discharge capacity apparently higher than the material of conventional solid phase method preparation; Fig. 5 shows that the prepared lithium manganese phosphate material 1C cycle performance of solid phase method that has increased the curing process step has obtained remarkable improvement.
Embodiment 2:
Take by weighing the 38.79g lithium carbonate earlier, the 245g manganese acetate, the ammonium phosphate of 213.28g, 5.10g aluminium oxide and 100.43g glucose, and above-mentioned raw materials is scattered in the deionized water of 1.5L; Carry out abundant ball milling then, the ball milling time is 10h, then the ball milling disposed slurry is transferred to and is carried out slaking in the electric heating stirred autoclave, and curing temperature is controlled at 70 ℃, and the curing time is 16h, and mixing speed is 60r/min; After treating that slaking finishes, slurry is carried out spray drying, under the nitrogen atmosphere protection, carry out high-temperature calcination then, calcining heat is 700, and calcination time is 8h, at last calcined product is pulverized and 300 orders that sieve get the product anode material for lithium-ion batteries.This material 1C discharge capacity first is 141mAh/g.
Embodiment 3:
Take by weighing the 79.18g lithium acetate earlier, the 245g manganese acetate, the 145.26g diammonium hydrogen phosphate, 0.403g magnesia and 140.95g polyvinyl alcohol, and above-mentioned raw materials is scattered in the deionized water of 1L; Carry out abundant ball milling then, the ball milling time is 15h, then the ball milling disposed slurry is transferred to and is carried out slaking in the electric heating stirred autoclave, and curing temperature is controlled at 30 ℃, and the curing time is 24h, and mixing speed is 20r/min; After treating that slaking finishes, slurry is carried out spray drying, under the nitrogen atmosphere protection, carry out high-temperature calcination then, calcining heat is 800 ℃, and calcination time is 2h, at last calcined product is pulverized and 300 orders that sieve get the product anode material for lithium-ion batteries.This material 1C discharge capacity first is 145mAh/g.
More than the preparation method of a kind of anode material for lithium-ion batteries provided by the invention has been carried out detailed introduction; Having used concrete example among this paper sets forth principle of the present invention and execution mode; The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection range of claim of the present invention.
Claims (10)
1. a method for preparing anode material of lithium-ion battery is characterized in that, comprising:
A) Li source compound, manganese source compound, P source compound and carbon-source cpd are scattered in the solvent, obtain mixed slurry;
B) slurry that step a) is obtained carries out the slaking operation;
C) the slurry calcining after the slaking that step b) is obtained obtains anode material for lithium-ion batteries.
2. preparation method according to claim 1 is characterized in that, said Li source compound, manganese source compound, P source compound are 0.90～1.20: 1.00～0.80: 1～1.10 in molar ratio.
3. preparation method according to claim 1 and 2 is characterized in that, said carbon-source cpd accounts for the 10wt%～30wt% of Li source compound, manganese source compound, P source compound quality summation.
4. preparation method according to claim 1 and 2 is characterized in that, said Li source compound is lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate, lithium phosphate, lithium dihydrogen phosphate or phosphoric acid hydrogen two lithiums.
5. preparation method according to claim 1 and 2 is characterized in that, said manganese source compound is manganese acetate, manganese sulfate, manganese oxalate, manganese nitrate, manganese dioxide, mangano-manganic oxide, manganese sesquioxide managnic oxide or manganous hydroxide.
6. preparation method according to claim 1 and 2 is characterized in that, said P source compound is ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid, lithium phosphate, lithium dihydrogen phosphate or phosphoric acid hydrogen two lithiums.
7. preparation method according to claim 1 and 2 is characterized in that, said carbon-source cpd is conductive black, CNT, acetylene black, Graphene, lactose, sucrose, ascorbic acid, phenolic resins, polyvinyl alcohol, glucose or polysaccharide.
8. preparation method according to claim 1 and 2 is characterized in that, the slaking operation in the said step b) is specially:
Mixed slurry under 30～80 ℃, is stirred 2～24h.
9. preparation method according to claim 8 is characterized in that, the speed of said stirring is 20～100r/min.
10. preparation method according to claim 1 and 2 is characterized in that, also is included in the said mixed slurry and adds doped metallic elements.
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| CN103346319A (en) * | 2013-07-04 | 2013-10-09 | 河北工业大学 | Preparation method of metal doped lithium manganese phosphate/graphene/carbon composite material |
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| CN104733730A (en) * | 2015-03-24 | 2015-06-24 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery cathode material as well as preparation method thereof and lithium ion battery |
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| CN107394157A (en) * | 2017-07-19 | 2017-11-24 | 长沙矿冶研究院有限责任公司 | A kind of method of modifying of the lithium-rich manganese-based anode material for lithium-ion batteries based on ascorbic acid |
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| CN108305703A (en) * | 2018-01-19 | 2018-07-20 | 林荣铨 | A kind of preparation and its application of medium temperature graphene/nickel composite conducting slurry |
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| CN103022486A (en) * | 2012-12-19 | 2013-04-03 | 中国科学院宁波材料技术与工程研究所 | Preparation method for anode material of lithium ion battery |
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| CN103346319A (en) * | 2013-07-04 | 2013-10-09 | 河北工业大学 | Preparation method of metal doped lithium manganese phosphate/graphene/carbon composite material |
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| CN104733730B (en) * | 2015-03-24 | 2017-10-03 | 中国科学院宁波材料技术与工程研究所 | A kind of anode material for lithium-ion batteries and preparation method thereof and lithium ion battery |
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| CN105206804A (en) * | 2015-08-31 | 2015-12-30 | 无锡市嘉邦电力管道厂 | Lithium ion battery and preparing method thereof |
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| CN107394157B (en) * | 2017-07-19 | 2020-07-10 | 长沙矿冶研究院有限责任公司 | Modification method of ascorbic acid-based lithium-rich manganese-based lithium ion battery positive electrode material |
| CN108231241A (en) * | 2018-01-19 | 2018-06-29 | 林荣铨 | The preparation and its application of a kind of medium temperature graphene/copper composite conducting slurry |
| CN108305703A (en) * | 2018-01-19 | 2018-07-20 | 林荣铨 | A kind of preparation and its application of medium temperature graphene/nickel composite conducting slurry |
| CN108305702A (en) * | 2018-01-19 | 2018-07-20 | 林荣铨 | A kind of preparation and its application of medium temperature graphene/silver composite conducting slurry |
| CN108305716A (en) * | 2018-01-19 | 2018-07-20 | 林荣铨 | A kind of preparation method of graphene conductive slurry and its conductive coating of preparation |
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