CN103199236A - Doped lithium manganate precursor, modified lithium manganate positive electrode material and preparation method thereof - Google Patents
Doped lithium manganate precursor, modified lithium manganate positive electrode material and preparation method thereof Download PDFInfo
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- CN103199236A CN103199236A CN2013101253718A CN201310125371A CN103199236A CN 103199236 A CN103199236 A CN 103199236A CN 2013101253718 A CN2013101253718 A CN 2013101253718A CN 201310125371 A CN201310125371 A CN 201310125371A CN 103199236 A CN103199236 A CN 103199236A
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- lithium manganate
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a doped lithium manganate precursor, a modified lithium manganate positive electrode material and a preparation method thereof. Firstly, metal manganese and doping metal are used for preparing a metal alloy according to a certain molar ratio, and then the metal alloy is fully oxidized to obtain the doped lithium manganate precursor. The preparation method of a lithium ion battery positive electrode material by utilizing the doped lithium manganate precursor comprises the following steps of: crushing the doped lithium manganate precursor; and adding 45%-50% by mole of lithium salt into the crushed precursor, then performing ball milling and drying, and then calcining to obtain an initial doped lithium manganate positive electrode material. The tap density of the modified lithium manganate positive electrode material is not less than 2.6g/cm<3>, a button cell produced by the product is tested, 1C charge and discharge are performed, and when the discharge achieves 2.4V, the reversible discharge capacity is 175mAh/g- 260mAh/g; and when the discharge achieves 2.75V, the reversible discharge capacity is 135mAh/g-185mAh/g.
Description
Technical field
The present invention relates to adulterated lithium manganate presoma, modification manganate cathode material for lithium and preparation method thereof.
Background technology
In the composition of lithium ion battery, positive electrode is the key that determines the lithium ion battery performance.In present commercial lithium ion battery, what positive electrode mainly adopted is cobalt acid lithium, ternary material (cobalt nickel LiMn2O4), LiMn2O4 and LiFePO 4.And characteristics such as LiMn2O4 is good because of aboundresources, low price, fail safe, non-environmental-pollution, manufacturing process are simple have relatively become the main selection of field power lithium-ion battery positive electrodes such as electric automobile, electric bicycle, electric tool.
LiMn2O4 has the LiMn of spinel structure
2O
4LiMnO with layer structure
2Two kinds, all adopt the LiMn of spinel structure in the commercial applications
2O
4Spinel structure LiMn
2O
4With respect to the embedding of lithium metal, take off the embedding current potential about 4V, theoretical capacity is 148mAh/g, and actual capacity is mostly at 100-120mAh/g.
Though LiMn2O4 has advantage, himself defective is also arranged, be mainly reflected in that specific capacity is lower, cycle life is short, capacity attenuation is serious in the high temperature charge and discharge cycles process.The root that these problems produce is that structural stability was relatively poor after manganate precursor for lithium (comprising manganese dioxide, manganese sesquioxide managnic oxide etc.) formed LiMn2O4 with lithium salts chemical combination.
In order to improve the structural stability of LiMn2O4, the researcher has adopted various technical schemes, for example: adopt chemical method to carry out bulk phase-doped to manganate precursor for lithium, add metal cation M(such as aluminium, cobalt, copper, nickel etc.) stablize lattice (be method that the Chinese patent of CN102201572A disclose a kind of doping vario-property as publication number); Improve manganate precursor for lithium and lithium salts synthetic method; LiMn2O4 is realized that the surface coats; Adopt Mn
3O
4Substitute MnO
2As the presoma of synthetic LiMn2O4 etc.But the improvement degree by these method gained modification lithium manganate battery its cycle lives of product and high-temperature behavior is limited, and can not improve the specific capacity of LiMn2O4, also produces the counter productive that reduces battery capacity mostly.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, provide a kind of adulterated lithium manganate presoma, modification manganate cathode material for lithium with and preparation method thereof.
For solving the problems of the technologies described above, the present invention has at first proposed a kind of preparation method of new adulterated lithium manganate presoma, may further comprise the steps:
At first with manganese metal and doping metals in molar ratio 1:0.02-1:0.35 make metal alloy, then described metal alloy is carried out complete oxidation, namely obtain the adulterated lithium manganate presoma, described doping metals is the metal of the existing related metal oxide correspondence of oxide-doped method.
The basis of above-mentioned presoma preparation method invention: existing LiMn2O4 doping vario-property adopts the chemical doping method mostly, namely how to obtain the oxide of doping metals and the homogeneous mixture of manganese oxide, and calcining forms presoma then.But activity and ideal value gap with the LiMn2O4 of this presoma preparation are bigger.Main cause is manganese oxide (manganese dioxide, manganese sesquioxide managnic oxide and mangano-manganic oxide), except forming the stable structure with alkali metal and alkaline earth oxide, all can not form stable compound with other metal oxides, in follow-up adding in the lithium sintering process, be easy to decompose, form crystal grain separately.Like this, LiMn2O4 crystal grain and the effect of blended metal oxide intergranule just only limit between the grain surface.And in the lithium ion battery course of work, lithium ion inserts, deviates from material lattice inside.The not satisfactory theoretical foundation of chemical doping effect that Here it is.
Adulterated lithium manganate presoma preparation method of the present invention is: at first obtain the alloy of doping metals and manganese metal, in this alloy, form atom level between doping metals and the manganese metal and evenly disperse; Then this alloy is carried out complete oxidation, form the adulterated lithium manganate presoma of compact structure.This presoma has following characteristic: (1) its tap density is mixed high more than 15% than chemical method; (2) blended metal oxide and manganese oxide disperse with small-sized uniform crystal particles, and the crystal grain activity is very high; (3) lattice is interlaced, causes the manganese oxide lattice to distort, and not only forms more polycrystalline lattice space, and makes the manganese oxide activity bigger.Therefore, with the not only cycle performance improvement of adulterated lithium manganate of this persursor material making, and capacity also increases substantially.
The described metal alloy of making in theory, can adopt any technology and the method that can form alloy.Preferably, employing comprises any one in following two kinds of processes:
One is fusion method.Manganese metal and doping metals are placed melting furnace by described mol ratio, charge into protective gas, be heated to 1250-1350 ° of C, insulation forms alloy.This method is simple, stable components and being uniformly dispersed.
The 2nd, powder metallurgic method.Manganese metal powder and doping metals powder are placed high speed ball mill by described mol ratio, charge into argon shield, dry ball milling reaches and fully mixes and preliminary alloying.The metal dust that mixes is positioned in the graphite jig, uses forcing press compression moulding.With the HIP sintering stove heating of argon shield, temperature reaches 800--1200 ° of C, is incubated 1-2 hour then.This method does not need to reach alloy melting point, but homogeneity of ingredients is not as the former.
Described metal alloy is carried out complete oxidation, in theory, can adopt burning method arbitrarily, be included in autoxidation in the air.Preferably, adopt the solid phase calcination method for oxidation, that is: in Muffle furnace, calcine metal alloy, utilize airborne oxygen to alloy oxidation, temperature 600-900 ° of C, the time is more than 10 hours.
Preferred to doping metals, the present invention has selected zinc, nickel, copper, indium, aluminium, cobalt, antimony, comprises that several in these metals arrange in pairs or groups by arbitrary proportion.The basic ideas of Xuan Zeing are like this: the first, and intensity and the fusing point of this metal are low; The second, the atomic weight of this metallic element is bigger than manganese; The 3rd, the oxide after the calcining of this metal want can with manganese oxide chemical combination; The 4th, this metal oxide will have certain activity.
Based on above-mentioned adulterated lithium manganate presoma, the present invention has further proposed a kind of adulterated lithium manganate positive electrode and preparation method thereof, may further comprise the steps:
Step 1, above-mentioned presoma is pulverized.Because be the metal calcining, particle size is excessive, as not pulverizing, lithium is difficult to diffusion evenly when adding the lithium calcining.And if lithium manganate particle is oversize, cohesive force is excessive, causes the lithium ion transport resistance excessive, influences chemical property.After presoma was pulverized, it was abundant to also help calcined oxide.
Above-mentioned presoma disintegrating process is: earlier broken to alloyed powder, and calcining then.Pulverizing is available high speed ball mill, also available other method.Preferable mode is that pulverizing, calcining are hocketed: after tentatively pulverizing alloy, calcining earlier used the high speed ball mill dry ball milling more than 0.5 hour more than 1 hour; Calcined 5-20 hour, dry ball milling is more than 0.5 hour more again; Continue calcining then, up to whole oxidations; Dry ball milling added the wet method ball milling 0.5-4 hour again, and is standby after oven dry, the screening.
Step 2, to add mol ratio in above-mentioned pulverizing presoma be the lithium salts of 45%-60%, comprises lithium hydroxide, lithium carbonate, lithium acetate.Then, after ball milling (wet-milling), the oven dry, 500 ℃ of-600 ℃ of calcination 1-10h of first low temperature in Muffle furnace, 700 ℃-900 ℃ high times of calcination 10-60h(temperature of high temperature suitably shorten again), obtain initial adulterated lithium manganate positive electrode.
Step 3: described initial adulterated lithium manganate positive electrode is pulverized again, oven dry, screening namely obtains required adulterated lithium manganate positive electrode.
As more optimal method, the preparation method of modification manganate cathode material for lithium of the present invention, also comprise step 4: with the prepared adulterated lithium manganate positive electrode of step 3, under 100 ℃ of-300 ℃ of temperature, with reducibility gas (as hydrogen, methane etc.) reduction 30-180 minute, obtain better modification manganate cathode material for lithium.Know-why of the present invention is, the described pulverizing presoma of step 2 adds behind the lithium salts in the calcination process, and the oxidized lithium of presoma lattice struts, the active increase, and lithia forms lithium peroxide by force to the oxygen attraction, thus in LiMn2O4, infiltrate a small amount of excessive oxygen.Though the amount of these oxygen seldom, have a strong impact on material capacity (lithium ion fills output to be reduced) and cycle performance.Remove the excess of oxygen of infiltrating in the LiMn2O4 so adopt reduction reaction.
The modification manganate cathode material for lithium of method for preparing, its tap density 〉=2.6g/cm
3, electrode is filled good processability.The button cell that this product is made detects, and 1C discharges and recharges, and when being discharged to 2.4 volts, its reversible discharge capacity is 175mAh/g-260mAh/g; When being discharged to 2.75 volts, reversible discharge capacity is 135mAh/g-185mAh/g.The theoretical capacity that has significantly exceeded existing spinel structure manganate lithium ion battery positive electrode 148mAh/g.Therefore have great commercial application prospect, application should be widely promoted.
Embodiment
A pair of the present invention further describes below in conjunction with the specific embodiment table, detailed, the complete preparation method who has described from preparation adulterated lithium manganate presoma to the modification manganate cathode material for lithium of embodiment.Concrete implementation step is as follows:
Step 1, doping metals in manganese metal and the table is made alloy by mol ratio shown in corresponding.Various equivalent modifications can be understood, and makes alloy and can adopt all methods that can form alloy.The concrete grammar that embodiment adopts comprises,
Method is 1.: doping metals in manganese metal and the table is put in corundum crucible, crucible is placed melting furnace, charge into the protective gas argon gas, be heated to 1250-1350 ° of C, be incubated 45 minutes.Perhaps,
Method is 2.: doping metals powder in manganese metal powder and the table is placed high speed ball mill, charge into argon shield, dry ball milling 2-3 hour.Metal dust behind the ball milling is positioned in the graphite jig, uses forcing press compression moulding.With the HIP sintering stove heating of argon shield, temperature reaches 800--1200 ° of C, is incubated 1-2 hour then.Alloy is taken out in the cooling back, and preliminary the pulverizing.
Step 2, to above-mentioned alloy oxidation.Various equivalent modifications can be understood, and can adopt existing all methods for alloy oxidation, even the air autoxidation.Based on the convenience of commercial application, the oxidation step that embodiment adopts is: to above-mentioned alloy calcined oxide, the programming rate with 5-10 ℃/min is warming up to 600 ℃-900 ℃ earlier, is incubated 2-3h then under the air atmosphere in Muffle furnace, takes out the back air cooling; With the material after the calcining with high speed ball mill dry ball milling 1-2 hour, again under the air atmosphere in Muffle furnace to alloy calcined oxide 12-15 hour, used the high speed ball mill dry ball milling again 1-2 hour; Continue calcined oxide to complete oxidation.
Step 3, preparation adulterated lithium manganate presoma powder.Concrete steps are: use the high speed ball mill dry ball milling after 1-2 hour the material of calcined oxide, and wet ball grinding 2-4 hour again; Dry bake out temperature 120-150 ℃ behind the ball milling; With the screening of 200 eye mesh screens, make adulterated lithium manganate presoma powder.
Step 4, the initial adulterated lithium manganate positive electrode of preparation.Concrete steps are: add lithium carbonate or lithium hydroxide by the mol ratio respective amount of lithium shown in the table in adulterated lithium manganate presoma powder; Add wet-milling with the high speed ball mill dry grinding, the ball milling time is 2-3 hour; Dry bake out temperature 120-150 ℃ behind the ball milling.Above-mentioned powder first programming rate with 5 ℃/min in Muffle furnace is warming up to 500-600 ℃, is incubated 1-10h then; Programming rate with 5 ℃/min is warming up to 700-900 ℃ again, insulation 10-60h; With the stove cooling, obtain initial adulterated lithium manganate positive electrode.
Step 5, the initial adulterated lithium manganate positive electrode in calcining back are pulverized again.Concrete steps are: after with high speed ball mill the resulting initial adulterated lithium manganate positive electrode of step 4 being pulverized again, and oven dry, screening, oven dry back moisture is lower than 1.5%, obtain the adulterated lithium manganate positive electrode, its particle mean size is 10-24 μ m, and it is as shown in the table for tap density.
Step 6, the adulterated lithium manganate positive electrode is carried out reduction reaction.Concrete steps are: the adulterated lithium manganate positive electrode is put in porcelain boat, porcelain boat is placed the normal pressure atmosphere furnace.Programming rate with 5 ℃/min is warming up to 100-300 ℃, charges into argon gas (normal pressure) simultaneously, and the time is half an hour.Change hydrogen (normal pressure) reduction 30-180 minute then into, lower the temperature with stove.Make the modification manganate cathode material for lithium.
Table one, specific embodiment table
It should be noted last that, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although with reference to preferred embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (7)
1. the preparation method of an adulterated lithium manganate presoma is characterized in that, may further comprise the steps:
At first with manganese metal and doping metals in molar ratio 1:0.02-1:0.35 make metal alloy, then described metal alloy is carried out complete oxidation, namely obtain the adulterated lithium manganate presoma, described doping metals is the metal of the existing related metal oxide correspondence of oxide-doped method.
2. adulterated lithium manganate presoma preparation method according to claim 1 is characterized in that, described doping metals is one of zinc, nickel, copper, indium, aluminium, cobalt, antimony, or several combination of described metal.
3. adulterated lithium manganate presoma preparation method according to claim 1 and 2, it is characterized in that, described metal alloy is carried out complete oxidation, adopt the solid phase calcination method for oxidation, that is: in Muffle furnace, calcine metal alloy, utilize airborne oxygen to alloy oxidation, temperature 600-900 ° of C, the time is more than 10 hours.
4. a preparation method who utilizes the modification manganate cathode material for lithium of described adulterated lithium manganate presoma is characterized in that, may further comprise the steps:
Step 1, described adulterated lithium manganate presoma is pulverized;
Step 2, to add mol ratio in above-mentioned pulverizing presoma be the lithium salts of 45%-60%, then after ball milling, the oven dry, first calcination 1-10h under 500 ℃ of-600 ℃ of temperature in Muffle furnace, calcination 10-60h under 700 ℃ of-900 ℃ of temperature obtains initial adulterated lithium manganate positive electrode again.
5. the preparation method who utilizes the modification manganate cathode material for lithium of described adulterated lithium manganate presoma according to claim 4, it is characterized in that, also comprise step 3: described initial adulterated lithium manganate positive electrode is pulverized oven dry again, screening namely obtains required adulterated lithium manganate positive electrode.
6. the preparation method who utilizes the modification manganate cathode material for lithium of described adulterated lithium manganate presoma according to claim 5, it is characterized in that, also comprise step 4: with the prepared adulterated lithium manganate positive electrode of step 3, under 100 ℃ of-300 ℃ of temperature, with reducibility gas reduction 30-180 minute, obtain the modification manganate cathode material for lithium.
7. a modification manganate cathode material for lithium is characterized in that, the tap density 〉=2.6g/cm of described modification manganate cathode material for lithium
3, the button cell that this product is made detects, and 1C discharges and recharges, and when being discharged to 2.4 volts, its reversible discharge capacity is 175mAh/g-260mAh/g; When being discharged to 2.75 volts, reversible discharge capacity is 135mAh/g-185mAh/g.
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Cited By (5)
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| CN104716315A (en) * | 2013-12-16 | 2015-06-17 | 青岛乾运高科新材料股份有限公司 | Preparation method of lithium ion batteries cathode material solid solution with core-shell structure |
| CN107994227A (en) * | 2017-12-16 | 2018-05-04 | 淄博国利新电源科技有限公司 | The preparation method of 523 ternary material precursor of zinc doping |
| CN111640934A (en) * | 2020-04-18 | 2020-09-08 | 浙江金鹰新能源技术开发有限公司 | High-temperature solid-phase sintering method for lithium ion anode material |
| CN112490436A (en) * | 2020-12-02 | 2021-03-12 | 湖北文理学院 | Preparation method of nickel-doped spinel lithium manganate serving as lithium ion battery anode material |
| CN114604899A (en) * | 2022-04-11 | 2022-06-10 | 安徽工业大学 | Lithium ion battery anode material precursor and preparation method thereof |
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| CN1562771A (en) * | 2004-04-07 | 2005-01-12 | 中信国安盟固利电源技术有限公司 | Spherical shaped lithium manganate and preparation method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104716315A (en) * | 2013-12-16 | 2015-06-17 | 青岛乾运高科新材料股份有限公司 | Preparation method of lithium ion batteries cathode material solid solution with core-shell structure |
| CN107994227A (en) * | 2017-12-16 | 2018-05-04 | 淄博国利新电源科技有限公司 | The preparation method of 523 ternary material precursor of zinc doping |
| CN111640934A (en) * | 2020-04-18 | 2020-09-08 | 浙江金鹰新能源技术开发有限公司 | High-temperature solid-phase sintering method for lithium ion anode material |
| CN112490436A (en) * | 2020-12-02 | 2021-03-12 | 湖北文理学院 | Preparation method of nickel-doped spinel lithium manganate serving as lithium ion battery anode material |
| CN112490436B (en) * | 2020-12-02 | 2023-02-03 | 湖北文理学院 | Preparation method of nickel-doped spinel lithium manganate serving as lithium ion battery anode material |
| CN114604899A (en) * | 2022-04-11 | 2022-06-10 | 安徽工业大学 | Lithium ion battery anode material precursor and preparation method thereof |
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