CN101582501B - Preparation method for composite anode material of high capacity lithium ion battery - Google Patents
Preparation method for composite anode material of high capacity lithium ion battery Download PDFInfo
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- CN101582501B CN101582501B CN2009103036127A CN200910303612A CN101582501B CN 101582501 B CN101582501 B CN 101582501B CN 2009103036127 A CN2009103036127 A CN 2009103036127A CN 200910303612 A CN200910303612 A CN 200910303612A CN 101582501 B CN101582501 B CN 101582501B
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Abstract
The invention discloses a preparation method for the composite anode material of a high capacity lithium ion battery. The chemical molecular formula of the composite anode material of the high capacity lithium ion battery is xLi [Li1/3 Mn2/3] O2. (1-x) Li [Ni1/3 Mn1/3Co1/3] O2; wherein x is larger than or equal to zero and less than or equal to one; the preparation method is as follows: a compound of nickel, cobalt and manganese and a lithium source compound are activated by the mechano-chemistry to be well blended by high-energy ball milling in a certain solvent medium; the obtained mixture is dried in the low temperature, placed in a muffle furnace to be roasted in the high temperature, and then is cooled into the room temperature to obtain the composite anode material of the lithium ion battery. The preparation method greatly lowers the preparation cost of the material. Compared with the prior art for compounding the composite anode material of the high capacity lithium ion battery, the preparation method has simple technological operation and control, is easy to be industrialized, and has very high promotional value.
Description
Technical field
The invention belongs to the lithium ion battery material technical field, relate to a kind of preparation method of composite anode material of high-capacity lithium ion battery.
Background technology
The extensive uses of portable type electronic product on market such as mobile phone, notebook computer, digital camera, electric tool have driven the fast development of lithium ion battery industry.At present, LiCoO
2Be still most widely used anode material for lithium-ion batteries, LiCoO
2Discharge platform high power capacity height, good cycle, and production technology is easy to control, and properties of product are stable.But because the Co scarcity of resources, cost an arm and a leg and poisonous, so Recent study person are seeking to substitute LiCoO always
2Other positive electrode.LiNiO
2And LiMn
2O
4Once once be considered to substitute preferably LiCoO
2Material, but LiNiO
2The synthesis condition harshness is difficult to realize industrialization, and itself there are problems such as security performance in this material, has hindered its practical application.LiMn
2O
4Then because good, the low price of its security performance, and belong to environment-friendly material and receive publicity, yet, this material capacity is low, and its theoretical capacity only is 148mAh/g, and prepared its reversible capacity of material can only reach about 110mAh/g usually, and in electrolyte, especially at high temperature, accelerate, be difficult to large-scale popularization and use owing to the dissolving of manganese causes the material loop attenuation.
Lithium ion battery in series composite positive pole xLi[Li
1/3Mn
2/3] O
2. (1-x) Li[Ni
1/3Mn
1/3Co
1/3] O
2Similar in LiCoO
2, belong to α-NaFeO that space group is the R-3m type
2The type layer structure has the capacity height, price is low, environmentally friendly, Heat stability is good, charges and discharge the advantage of voltage wide ranges, is considered to be hopeful most to replace at present LiCoO
2One of candidate's positive electrode.In the last few years, Li[Ni
xLi
1/3-2x/3Mn
2/3-x/3] O
2Material makes more scholars' further research because of it has higher charge/discharge capacity, but the electronic conductivity of this material is not high, and the doping cobalt element is one of the effective ways that improve the electronic conductivity of this material.XLi[Li
1/3Mn
2/3] O
2. (1-x) Li[Ni
1/3Mn
1/3Co
1/3] O
2About 4.6V, there is one during the composite positive pole first charge-discharge and takes off the platform that lithium is followed deoxidation, Li in this process
2MnO
3Component has obtained activation, thereby makes this material show higher specific capacity in discharge process, simultaneously Li
2MnO
3Component has also played the effect of stabilized electrodes structure in charge and discharge process.Therefore, xLi[Li
1/3Mn
2/3] O
2. (1-x) Li[Ni
1/3Mn
1/3Co
1/3] O
2Material becomes this domain expert scholar's research focus gradually with high power capacity, low cost, be subjected to paying close attention to widely than the stable structure advantage in the stratified material system.
At present, lithium ion composite positive pole xLi[Li
1/3Mn
2/3] O
2. (1-x) Li[Ni
1/3Mn
1/3Co
1/3] O
2What preparation was adopted all is coprecipitation: 1. the hydroxide presoma for preparing the composite transition metal ion; 2. presoma is joined lithium and carry out roasting again.Though this preparation method can improve the even distribution of ion, but also exist some obvious defects, as: Ni, Co, the different supersaturation of Mn hydroxide can cause the poor repeatability of coprecipitation process operation in the hydroxide system, cause presoma phase composition fluctuation, make that the performance difference of product is very big; In precipitation process, as not strict control experiment condition, then the M2+ in the hydroxide is easy to oxidizedly, and then causes the oxide dephasign that occurs different valence state manganese in the end product, has influenced the chemical property of this material to a certain extent; Coprecipitation preparation technology is comparatively complicated, and controlled condition is also comparatively complicated simultaneously.In sum, the xLi[Li that studies at present
1/3Mn
2/3] O
2. (1-x) Li[Ni
1/3Mn
1/3Co
1/3] O
2The preparation method of positive electrode has limited the suitability for industrialized production and the practical application of this material to a certain extent, therefore press for a kind of operation good reproducibility, technology is simple, and preparation method with low cost promotes this material with very big application prospect and market potential to put into production use as early as possible.
Summary of the invention
The objective of the invention is to solve coprecipitation and prepare composite anode material of high-capacity lithium ion battery xLi[Li
1/3Mn
2/3] O
2. (1-x) Li[Ni
1/3Mn
1/3Co
1/3] O
2Technology and preparation condition complicated problems provide a kind of preparation method of composite anode material of high-capacity lithium ion battery, and preparation technology is simple for this method, are easy to control, and the operation good reproducibility does not need harsh outside subsidiary conditions, and production cost is low.
For achieving the above object, technical scheme of the present invention is:
A kind of preparation method of composite anode material of high-capacity lithium ion battery is characterized in that, may further comprise the steps:
1) mole metering ratio is (1-a): (1-a): (1+a): the compound of the compound of nickel (3+a), the compound of cobalt, manganese and lithium salts add the ball milling solvent medium that volume is 1～5 times of a mixed material volume in the lump and (activate by mechanochemistry, be the effect of existing mechanical force, chemical reaction take place again simultaneously) carry out ball milling and evenly mix; 0≤a≤1 wherein;
2) with the mixture oven dry that obtains behind the ball milling;
3) baking mixture 100～400 orders are sieved the back roasting, sintering temperature is 600 ~ 1200 ℃, promptly gets xLi[Li after the cooling
1/3Mn
2/3] O
2. (1-x) Li[Ni
1/3Mn
1/3Co
1/3] O
2Lithium ion battery composite cathode material, 0≤x≤1.
Described lithium salts is one or more in lithium chloride, lithium sulfate, lithium carbonate, lithium acetate, the lithium hydroxide; The compound of described nickel is one or more in nickel chloride, nickelous sulfate, nickelous carbonate, nickel acetate, nickel protoxide, nickel sesquioxide, hickelous nydroxide, the nickel hydroxide; The compound of cobalt is one or more in cobalt chloride, cobaltous sulfate, cobalt carbonate, cobalt acetate, cobalt oxide, cobalt protoxide, the cobaltosic oxide; The compound of manganese is one or more in manganese chloride, manganese sulfate, manganese carbonate, manganese acetate, manganese dioxide, the mangano-manganic oxide; Described ball milling solvent medium adopts one or more in water, alcohol, acetone, isopropyl alcohol, ether, butanone, the EGME.
The rotating speed of ball milling described in the step 1) is 100 ~ 1000r/min, and the ball milling time is 1 ~ 48h.
Step 2) time of oven dry is 8～24h in.
Roasting process in the step 3) is: the programming rate with 1 ~ 60 ℃/min is warmed up to 600 ~ 1200 ℃, insulation 1 ~ 48h, and the cooling procedure in the step 3) is for naturally cooling to room temperature.
Advantage of the present invention and effect:
Preparation method of the present invention is to be raw material with the compound of nickel, cobalt, manganese and lithium salts, mixes back sintering and cool off the xLi[Li that utilizes preparation method of the present invention to synthesize with stove under normal air atmosphere through mechanochemistry activation ball milling
1/3Mn
2/3] O
2. (1-x) Li[Ni
1/3Mn
1/3Co
1/3] O
2In the voltage range of 2 ~ 4.8V, specific discharge capacity reaches 180～250mAh/g, and good cycle.Compare with the technology of this composite anode material of high-capacity lithium ion battery of existing preparation, the composite anode material of high-capacity lithium ion battery of the inventive method preparation is keeping having simplified preparation method and processing step greatly on the constant or basis that increases of material electrochemical performance.Method technology of the present invention is simple, be easy to control, and the operation good reproducibility does not need harsh outside subsidiary conditions, is easy to industrialization.Because work simplification, this method can reduce the production cost of anode material for lithium-ion batteries greatly, has very high promotional value.
Description of drawings
Fig. 1 is the composite anode material of high-capacity lithium ion battery SEM figure of the embodiment of the invention 1;
Fig. 2 is the composite anode material of high-capacity lithium ion battery XRD figure of the embodiment of the invention 4;
The composite anode material of high-capacity lithium ion battery first charge-discharge curve chart of Fig. 3 embodiment of the invention 1 discharges and recharges at ambient temperature, and electrolyte adopts 1mol/L LiPF
6/ EC: DMC (1: 1), voltage range 2～4.8V, charge-discharge magnification 0.2C;
The composite anode material of high-capacity lithium ion battery cycle performance figure of Fig. 4 embodiment of the invention 4 discharges and recharges at ambient temperature, and electrolyte adopts 1mol/L LiPF
6/ EC: DMC (1: 1), voltage range 2～4.8V, charge-discharge magnification 0.2C.
Embodiment
The present invention is further illustrated below in conjunction with the drawings and specific embodiments.
Embodiment 1
With nickel hydroxide 37.841 grams, cobalt acetate 101.669 grams, mangano-manganic oxide 124.528 grams, lithium carbonate 133.121 grams and adding volume are that the acetone of 1 times of mixed material volume carries out the ball milling mixing, behind spend the night oven dry, crushing screening presoma is placed the Muffle furnace roasting, reaction temperature is 1200 ℃, and the reaction time is 1 hour, be cooled to room temperature then the sample taking-up is pulverized, make 0.6Li[Li
1/3Mn
2/3] O
2.0.4Li[Ni
1/3Mn
1/3Co
1/3] O
2Composite positive pole.Fig. 1 is the SEM figure of this material, schemes from SEM that the gained material granule is tiny evenly as can be seen, and reunion is to a certain degree arranged.Fig. 3 is its first charge-discharge curve chart, and the first discharge specific capacity that shows this material is 203mAh/g.
With nickel sesquioxide 67.5 grams, cobalt oxide 66.41 grams, manganese carbonate 146.507 grams, lithium acetate 329.729 grams and adding volume are that the alcohol of 1.5 times of mixed material volumes carries out the ball milling mixing, behind spend the night oven dry, crushing screening presoma is placed the Muffle furnace roasting, reaction temperature is 800 ℃, and the reaction time is 20 hours, be cooled to room temperature then the sample taking-up is pulverized, make 0.2Li[Li
1/3Mn
2/3] O
20.8Li[Ni
1/3Mn
1/3Co
1/3] O
2Composite positive pole.The first charge-discharge capacity of this material reaches 307.7mAh/g and 200.3mAh/g respectively.
Embodiment 3
With nickelous carbonate 72.68 grams, cobalt carbonate 72.814 grams, manganese acetate 346.592 grams, lithium hydroxide 155.1 grams and adding volume are that the isopropyl alcohol of 2 times of mixed material volumes carries out the ball milling mixing, behind spend the night oven dry, crushing screening presoma is placed the Muffle furnace roasting, reaction temperature is 1000 ℃, and the reaction time is 10 hours, be cooled to room temperature then the sample taking-up is pulverized, make 0.4Li[Li
1/3Mn
2/3] O
2.0.6Li[Ni
1/3Mn
1/3Co
1/3] O
2Composite positive pole.The first charge-discharge capacity of this material reaches 280mAh/g and 203mAh/g respectively.
With nickel acetate 50.788 grams, cobalt protoxide 15.137 grams, manganese chloride 238.623 grams, lithium carbonate 117.693 grams and adding volume are that the ether of 3 times of mixed material volumes carries out the ball milling mixing, behind spend the night oven dry, crushing screening presoma is placed the Muffle furnace roasting, reaction temperature is 600 ℃, and the reaction time is 48 hours, be cooled to room temperature then the sample taking-up is pulverized, make 0.8Li[Li
1/3Mn
2/3] O
2.0.2Li[Ni
1/3Mn
1/3Co
1/3] O
2Composite positive pole.The circulation volume first of this material is 209mAh/g, and through 32 circulations, capacity is almost undamped.Fig. 2 is the XRD figure of gained material, and this figure shows that this material is Li[Ni
1/3Mn
1/3Co
1/3] O
2With Li[Li
1/3Mn
2/3] O
2Compound.Fig. 4 is the cycle performance figure of gained material.
Embodiment 5
With nickel protoxide 30.494 grams, cobaltous sulfate 113.436 grams, manganese dioxide 163.65 grams, lithium chloride 155.906 grams and adding volume are that the acetone of 4 times of mixed material volumes carries out the ball milling mixing, behind spend the night oven dry, crushing screening presoma is placed the Muffle furnace roasting, reaction temperature is 1200 ℃, and the reaction time is 1 hour, be cooled to room temperature then the sample taking-up is pulverized, make 0.6Li[Li
1/3Mn
2/3] O
2.0.4Li[Ni
1/3Mn
1/3Co
1/3] O
2Composite positive pole.The first charge-discharge capacity of this material reaches 308.3mAh/g and 200.6mAh/g.
With nickelous sulfate 52.702 grams, cobaltosic oxide 16.07 grams, manganese carbonate 211.114 grams, lithium hydroxide 167.76 grams and adding volume are that the ether of 5 times of mixed material volumes carries out the ball milling mixing, behind spend the night oven dry, crushing screening presoma is placed the Muffle furnace roasting, reaction temperature is 600 ℃, and the reaction time is 48 hours, be cooled to room temperature then the sample taking-up is pulverized, make 0.8Li[Li
1/3Mn
2/3] O
2.0.2Li[Ni
1/3Mn
1/3Co
1/3] O
2Composite positive pole.The first charge-discharge capacity of this material reaches 282.4mAh/g and 195.2mAh/g.
Claims (4)
1. the preparation method of a composite anode material of high-capacity lithium ion battery is characterized in that, may further comprise the steps:
1) with mole metering than being (1-a): (1-a): (1+a): it is that the ball milling solvent medium of 1～5 times of mixed material volume carries out ball milling and evenly mixes that the compound of the compound of nickel (3+a), the compound of cobalt, manganese and lithium salts add volume in the lump; 0≤a≤1 wherein;
2) with the mixture oven dry that obtains behind the ball milling;
3) baking mixture 100～400 orders are sieved the back roasting, sintering temperature is 600～1200 ℃, promptly gets xLi[Li after the cooling
1/3Mn
2/3] O
2(1-x) Li[Ni
1/3Mn
1/3Co
1/3] O
2Lithium ion battery composite cathode material, 0≤x≤1;
Described lithium salts is one or more in lithium chloride, lithium sulfate, lithium carbonate, lithium acetate, the lithium hydroxide; The compound of described nickel is one or more in nickel chloride, nickelous sulfate, nickelous carbonate, nickel acetate, nickel protoxide, nickel sesquioxide, hickelous nydroxide, the nickel hydroxide; The compound of cobalt is one or more in cobalt chloride, cobaltous sulfate, cobalt carbonate, cobalt acetate, cobalt oxide, cobalt protoxide, the cobaltosic oxide; The compound of manganese is one or more in manganese chloride, manganese sulfate, manganese carbonate, manganese acetate, manganese dioxide, the mangano-manganic oxide; Described ball milling solvent medium adopts one or more in water, alcohol, acetone, isopropyl alcohol, ether, butanone, the ethylene glycol-methyl ether.
2. according to the preparation method of the described composite anode material of high-capacity lithium ion battery of claim 1, it is characterized in that the rotating speed of ball milling described in the step 1) is 100～1000r/min, the ball milling time is 1～48h.
3. according to the preparation method of the described composite anode material of high-capacity lithium ion battery of claim 1, it is characterized in that step 2) in the oven dry time be 8～24h.
4. according to the preparation method of each described composite anode material of high-capacity lithium ion battery of claim 1～3, it is characterized in that, roasting process in the step 3) is: the programming rate with 1～60 ℃/min is warmed up to 600～1200 ℃, insulation 1～48h, the cooling procedure in the step 3) is for naturally cooling to room temperature.
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| CN102169979A (en) * | 2010-02-26 | 2011-08-31 | 比亚迪股份有限公司 | Activating method of cathode material |
| CN104157870A (en) * | 2014-08-13 | 2014-11-19 | 青岛乾运高科新材料股份有限公司 | Two-step high-energy ball milling method for preparation of lithium manganate solid solution anode material rich in lithium |
| CN107403918A (en) * | 2017-07-26 | 2017-11-28 | 青岛大学 | A kind of preparation method for coating nitrogen-doped graphene ternary material |
| CN111634959A (en) * | 2020-06-02 | 2020-09-08 | 惠州亿纬锂能股份有限公司 | Ternary material, preparation method thereof and application of ternary material in lithium ion battery |
| CN114975985A (en) * | 2022-06-29 | 2022-08-30 | 三明市新能源产业技术研究院有限公司 | Ti-Cr co-doped high-voltage spinel cathode material, preparation method thereof, lithium ion battery cathode and lithium ion battery |
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