CN103618080A - Pretreatment method of cobaltosic oxide for preparing high-voltage lithium cobalt oxide, high-voltage lithium cobalt oxides anode material and preparation method of high-voltage lithium cobalt oxide - Google Patents
Pretreatment method of cobaltosic oxide for preparing high-voltage lithium cobalt oxide, high-voltage lithium cobalt oxides anode material and preparation method of high-voltage lithium cobalt oxide Download PDFInfo
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Abstract
The invention discloses a pretreatment method of cobaltosic oxide. The method comprises the steps of mixing a titanium-containing organic matter with an organic solvent so as to obtain a mixed liquid; adding cobaltosic oxide powder into the mixed liquid under a stirring condition so as to form a turbid liquid, adding deionized water into the turbid liquid, adequately stirring the turbid liquid and the deionized water until a uniform pulp-shaped fluid material is formed, and drying the uniform pulp-shaped fluid material so as to obtain a cobaltosic oxide compound. The high-voltage lithium cobalt oxide can be obtained by adequately mixing the obtained cobaltosic oxide compound, a lithium source and a dopant to obtain a mixture, and performing solid sintering and covering on the mixture at a high temperature. The tap density of the prepared high-voltage lithium cobalt oxide is more than 3.0g/cm<3>, the compaction density is more than 4.2g/cm<3>, the primary discharge gram capacity in the range of 2.8V to 4.34V can reach more than 164mAh/g, and the circulating capacity retention rate in 300 weeks is more than 89 percent. The prepared high-voltage lithium cobalt oxide has the advantages of good processing performance, high tap density, good circulating performance, high specific capacity and the like.
Description
Technical field
The preparing technical field that the invention belongs to new forms of energy conversion and storing technology and Related product, relates in particular to a kind of anode material for lithium-ion batteries and preparation method thereof.
Background technology
Lithium ion battery is the chargeable battery of new generation growing up the nineties in 20th century, because of plurality of advantages such as volume are little, lightweight, specific energy large, be easy to carry, on portable type electronic product and Move tool, obtains extensive use.
Cobalt acid lithium has many advantages of not replacing as the commercial anode material for lithium-ion batteries of the first generation: operating voltage higher (average working voltage is 3.7V) for example, charging/discharging voltage is steady, specific energy is high, good cycle, conductivity is high, and production technology is simple, easily prepares etc., can say, cobalt acid lithium is the most ripe, the longest anode material for lithium-ion batteries of commercialization time now.Yet, due to factors such as microstructures, Li
1-xcoO
2de-embedding coefficient must meet x≤0.5, otherwise the de-embedding meeting of too much lithium is caved in material internal structure, and capacity declines rapidly, and cycle performance also sharply declines thereupon.Although cobalt acid lithium has the theoretical capacity of 274mAh/g, deep discharge can cause caving in of structure, and actual gram volume performance at present only has 140mAh/g～150mAh/g.
Further miniaturization and multifunction along with portable electronics such as mobile phone, notebook computer, video cameras, requirement to battery output energy density is more and more higher, conventional cobalt acid lithium can not meet the requirement of the volume capacity density improving constantly, research discovery, improving the charging voltage of positive electrode and then improving lithium ion battery volume energy density becomes a kind of effective way.Existing lithium ion battery discharge and recharge interval substantially between 3.0V～4.2V, and take lithium ion cell charging that cobalt acid lithium is positive electrode, can increase the capacity of 14.0% left and right during to 4.4V, but its cyclical stability of lithium ion battery, thermal stability and security performance under 4.4V high voltage all can obviously decline.Therefore, how to improve the stability of cobalt acid lithium under high voltage and become the key technical problem that this area need to solve.
CN1697212A Chinese patent literature and US6555269B2 american documentation literature are all mentioned element dopings such as adopting Mg, Ti, to improve high-temperature behavior and the anti-over-charging performance of cobalt acid lithium; At non-patent literature (" Study of electrochemical properties of coating ZrO
2on LiCoO
2" .Journal of Alloys and Compounds, 496 (2010) 512-516) in also propose to have improved after coated zirconia the high temperature charge-discharge performance of cobalt acid lithium.CN101872859A Chinese patent literature adopts the liquid-phase hydrolysis precipitation method to make the Ti in solution
4+or Zr
4+precipitation, to the surface of cobalt acid lithium, is realized the coated of cobalt acid lithium, improves cycle characteristics and the anti-overshoot characteristics of material.In the patent documentation of having delivered at present, mainly concentrate on to adopt cobalt acid lithium is adulterated and finished product cobalt acid lithium carried out to coated method and improve the combination property of material under high voltage, but it is less to realize the report of the stability of material under high voltage that raw material is first carried out to preliminary treatment.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, a kind of preprocess method of cobaltosic oxide of the lithium ion anode material high voltage cobalt acid lithium that can be used for processability excellence is provided, also provide that a kind of equipment requirement is not high, simple to operate, automaticity is high, waste of raw materials is few, energy consumption is low and the preparation method of the lithium ion anode material high voltage cobalt of product quality excellent performance acid lithium, and correspondingly provide that a kind of good processability, tap density are high, good cycle, lithium ion anode material high voltage cobalt acid lithium that specific capacity is high.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of preprocess method of cobaltosic oxide for high voltage cobalt acid lithium of preparing, and comprises the following steps:
(1.1) take titaniferous organic substance introduces source as titanium ion, makes itself and immiscible organic solvent, forms the titaniferous organic substance mixed liquor of clarification;
(1.2) under stirring condition, cobaltosic oxide powder is added in described titaniferous organic substance mixed liquor, form suspension-turbid liquid, and continue stirring until evenly;
(1.3) in above-mentioned suspension-turbid liquid, add deionized water, until form milky suspension-turbid liquid, be stirred well to again and form even pulpous state fluid foods, then dry (for example can preferably in the mixing equipment with drying function, dry), complete coated preliminary treatment, obtain cobaltosic oxide compound.
In above-mentioned preprocess method, preferred, described titaniferous organic substance comprises one or more in butyl titanate, tetraethyl titanate, tetraisopropyl titanate, metatitanic acid n-propyl; The percentage that in described suspension-turbid liquid, titaniferous organic substance accounts for cobaltosic oxide and the organic gross mass of titaniferous is preferably 0.1w t%～10wt%.
In above-mentioned preprocess method, described organic solvent is preferably methyl alcohol, ethanol or isopropyl alcohol, and the volume ratio of described titaniferous organic substance and organic solvent is preferably controlled as 1:1～1:100.
In above-mentioned preprocess method, preferred, in described step (1.2), the lasting mixing time forming after suspension-turbid liquid is controlled as 15min～150min.
In above-mentioned preprocess method, preferred, in described step (1.3), being stirred well to and forming the required mixing time of even pulpous state fluid foods is 15min～150min.
In above-mentioned preprocess method, preferred, in described step (1.3), the volume ratio of the titaniferous organic substance mixed liquor of sneaking in the deionized water adding and suspension-turbid liquid is controlled at (0.5～1): (1～10).
In the technical scheme of the invention described above, by raw material cobaltosic oxide is coated to preliminary treatment, at the coated uniform titanium-containing compound of one deck in cobaltosic oxide surface, can make titanium elements enter more equably cobalt acid lithium lattice, and then can stable crystal structure in high-tension situation, prevent caving in of crystal structure that deep discharge causes.
As a total technical conceive, the present invention also provides a kind of preparation method of lithium ion anode material high voltage cobalt acid lithium, comprises the following steps:
(1) batching is mixed: cobaltosic oxide compound, lithium source and the alloy that above-mentioned preprocess method is obtained fully mixes (generally selecting high speed ball milling to mix) and obtain compound;
(2) high temperature solid-phase sintering: gained compound is carried out to high temperature solid-phase sintering, obtain cobalt acid lithium matrix;
(3) coated high-temperature process: carry out high-temperature process and make cobalt acid lithium matrix outer cladding form layer of metal oxide on the cobalt acid lithium matrix of gained, obtain high voltage cobalt acid lithium.
In above-mentioned preparation method, preferred, in described step (1), lithium source comprises one or more in lithium hydroxide, lithium carbonate, lithium oxalate, and the mol ratio of wherein controlling Li: Co is 0.95～1.2; Described alloy comprises oxide, hydroxide or the meta-aluminate of doped chemical, and doped chemical comprises one or more in Mg, Ti, Zr, Al, La; The doping of doped chemical is that 0.1wt%～2.0wt%(doping refers to the shared mass fraction of all doped chemicals in sintered products, according to can instead pushing away and draw the addition of alloy in preparation process the design of doping).
In above-mentioned preparation method, preferred, in described step (2), the sintering temperature of high temperature solid-phase sintering is controlled at 900 ℃～1500 ℃, and sintering time is controlled as 5h～25h.
In above-mentioned preparation method, preferred, in described step (3), described metal oxide is the oxide (the more preferably oxide of Zr, Al) of one or more elements in Mg, Ti, Zr, Al, La; The covering amount of described metal oxide (metal oxide accounts for the quality of cobalt acid lithium matrix) is 0.1wt%～1wt%.Preferred, in described step (3), the treatment temperature of coated high-temperature process is 500 ℃～1000 ℃, and the processing time is 5h～25h.By add metal oxide in cobalt acid lithium matrix batch mixing process, then carry out high-temperature process, effectively guaranteed the uniformity that metal oxide distributes at cobalt acid lithium matrix surface.
As a total technical conceive, the lithium ion anode material high voltage cobalt acid lithium that the present invention also provides a kind of above-mentioned preparation method to obtain, the median particle diameter D of described high voltage cobalt acid lithium
50be 10～20 μ m, tap density is 3.0g/cm
3above, compacted density is at 4.2g/cm
3above, in the scope of 2.8V～4.35V, 1C discharges more than gram volume reaches 164mAh/g first, and within 300 weeks, circulation volume conservation rate is more than 89%.
By above preparation technology of the present invention, can obtain the high voltage cobalt acid lithium product of above-mentioned specific median particle diameter, specific density, experiment and research show, suitable particle size range is most important for high voltage cobalt acid lithium material, the too little meeting of granularity causes electrolyte to the large area corrosion of crystal grain surface, the cobalt ions being dissolved in electrolyte increases, capacity attenuation is too fast, and compacted density is on the low side; Although and granularity is conducive to improve too greatly material compacted density, capacity performance is limited, therefore suitable particle size range is to guarantee that under high-voltage state material has the key factor of higher capacity and cycle performance.
Compared with prior art, the invention has the advantages that:
(1) the present invention, by cobaltosic oxide is carried out to preliminary treatment, has effectively improved the uniformity of material, has increased the stability of positive electrode crystal structure under high-voltage state.
(2) by material particle size being controlled and cobalt acid lithium matrix being coated to processing, reduce the dissolving of cobalt acid lithium cobalt under high voltage, guaranteed specific capacity and the cycle performance of cobalt acid lithium product under high-voltage state.
(3) the present invention merges the double sintering of coated metal oxide and cobalt acid lithium on cobalt acid lithium matrix to process, and has directly proposed the implementation step of coated high-temperature process, and this has not only strengthened the covered effect of metal oxide, and has effectively reduced the energy consumption of technique.
(4) the high voltage cobalt that prepared by the inventive method acid lithium product good processability, tap density are high, under the discharge voltage of>=4.3V, have good cycle performance and gram volume, and wherein gram volume is up to 160mAh/g～180mAh/g, and compacted density is at 4.2g/cm
3above.
(5) preparation method of the present invention is less demanding to synthesis device, simple to operate, can realize increasingly automatedly, and waste of raw materials is few, is applicable to very much suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the lithium ion anode material high voltage cobalt acid lithium that makes of the embodiment of the present invention 1.
The cyclic curve figure of the lithium ion battery that the anode material for lithium-ion batteries high voltage cobalt acid lithium that Fig. 2 is the employing embodiment of the present invention is made into.
Embodiment
Below in conjunction with Figure of description, the invention will be further described with concrete preferred embodiment, but protection range not thereby limiting the invention.
Embodiment 1:
A preparation method for high voltage lithium cobaltate cathode material of the present invention, comprises the following steps:
(1) the coated preliminary treatment of cobaltosic oxide: tetraisopropyl titanate and absolute ethyl alcohol is miscible, and the volume ratio of tetraisopropyl titanate and absolute ethyl alcohol is controlled as 1:10, forms the tetraisopropyl titanate mixed liquor of clarification; Under the state stirring, the powder of cobaltosic oxide is added in tetraisopropyl titanate mixed liquor, form suspension-turbid liquid, and continue stirring 30min to evenly, in suspension-turbid liquid, to account for the percentage of the gross mass of cobaltosic oxide and tetraisopropyl titanate be 0.1wt% to tetraisopropyl titanate; Then in the suspension-turbid liquid after mixing, dropwise add deionized water, the volume ratio of the tetraisopropyl titanate mixed liquor of sneaking in the deionized water dripping and suspension-turbid liquid is 1: 1, until form after even milky suspension-turbid liquid, stir again 30min, then be dried, obtain cobaltosic oxide compound standby;
(2) batching: by the cobaltosic oxide compound obtaining after dry and lithium carbonate, Mg (OH)
2and La
2o
3prepare burden, the mol ratio of wherein controlling Li:Co is that the doping of 1.06, Mg and La is respectively 0.15wt% and 0.05wt%, according to this doping, can determine Mg (OH)
2and La
2o
3addition in batching;
(3) high temperature solid-phase sintering: the compound obtaining in step (2) is placed in to pushed bat kiln and carries out high temperature solid-phase sintering, sintering temperature is 1000 ℃, and sintering time is 12h, obtains cobalt acid lithium matrix;
(4) coated high-temperature process: after the cobalt acid lithium matrix obtaining in step (3) is pulverized, add the ZrO of its mass fraction 1wt%
2, after high speed mixer mixes, double sintering at 800 ℃ of temperature (i.e. coated high-temperature process), sintering time is 12h, on cobalt acid lithium matrix, forms the uniform metal oxide ZrO of one deck
2, the product obtaining, with the cooling rear fragmentation of stove, is high voltage lithium cobaltate cathode material.
After testing, the anode material for lithium-ion batteries high voltage cobalt acid lithium that the preparation method of the present embodiment obtains as shown in Figure 1, its median particle diameter D
50be 17 μ m, tap density reaches 3.0g/cm
3, compacted density can reach 4.3g/cm
3; As shown in Figure 2, in the scope of 2.8V～4.35V, the 1C gram volume that discharges first reaches 168mAh/g, and within 300 weeks, circulation volume conservation rate is 90.2%.
Embodiment 2:
A preparation method for high voltage lithium cobaltate cathode material of the present invention, comprises the following steps:
(1) the coated preliminary treatment of cobaltosic oxide: tetraisopropyl titanate and absolute ethyl alcohol is miscible, and it is 1: 20 that the volume ratio of tetraisopropyl titanate and absolute ethyl alcohol is controlled, and forms the tetraisopropyl titanate mixed liquor of clarification; Under the state stirring, the powder of cobaltosic oxide is added in tetraisopropyl titanate mixed liquor, form suspension-turbid liquid, and continue to stir 30min extremely evenly; In suspension-turbid liquid, to account for the percentage of the gross mass of cobaltosic oxide and tetraisopropyl titanate be 0.1wt% to tetraisopropyl titanate; Then in the suspension-turbid liquid after mixing, dropwise add deionized water, the volume ratio of the tetraisopropyl titanate mixed liquor of sneaking in the deionized water dripping and suspension-turbid liquid is 1: 1, until form after even milky suspension-turbid liquid, stir again 30min, then be dried, obtain cobaltosic oxide compound standby;
(2) batching: by the cobaltosic oxide compound and lithium carbonate, MgO and the TiO that obtain after dry
2prepare burden, the mol ratio of wherein controlling Li:Co is that the doping of 1.02, Mg and Ti is respectively 0.5wt% and 0.1wt%;
(3) high temperature solid-phase sintering: the compound obtaining in step (2) is placed in to pushed bat kiln and carries out high temperature solid-phase sintering, sintering temperature is 1300 ℃, and sintering time is 12h, obtains cobalt acid lithium matrix;
(4) coated high-temperature process: after the cobalt acid lithium matrix obtaining in step (3) is pulverized, add the ZrO of its mass fraction 1wt%
2, after high speed mixer mixes, double sintering at 800 ℃ of temperature (i.e. coated high-temperature process), sintering time is 12h, on cobalt acid lithium matrix, forms the uniform metal oxide ZrO of one deck
2, the product obtaining, with the cooling rear fragmentation of stove, is high voltage lithium cobaltate cathode material.
The median particle diameter D of the anode material for lithium-ion batteries high voltage cobalt acid lithium that after testing, the preparation method of the present embodiment obtains
50be 15 μ m, tap density reaches 3.0g/cm
3, compacted density can reach 4.2g/cm
3; As shown in Figure 2, in the scope of 2.8V～4.35V, the 1C gram volume that discharges first reaches 165mAh/g, and within 300 weeks, circulation volume conservation rate is 89.6%.
Embodiment 3:
A preparation method for high voltage lithium cobaltate cathode material of the present invention, comprises the following steps:
(1) the coated preliminary treatment of cobaltosic oxide: butyl titanate solution and absolute ethyl alcohol is miscible, and the volume ratio of butyl titanate and absolute ethyl alcohol is controlled as 1:50, forms the butyl titanate mixed liquor of clarification; Under the state stirring, the powder of cobaltosic oxide is added in butyl titanate mixed liquor, form suspension-turbid liquid, and continue to stir 30min extremely evenly; In suspension-turbid liquid, to account for the percentage of the gross mass of cobaltosic oxide and butyl titanate be 10wt% to butyl titanate; Then in the suspension-turbid liquid after mixing, dropwise add deionized water, the volume ratio of the butyl titanate mixed liquor of sneaking in the deionized water dripping and suspension-turbid liquid is 1:1, until form after even milky suspension-turbid liquid, then stir 30min, then be dried, obtain cobaltosic oxide compound standby;
(2) batching: by the cobaltosic oxide compound obtaining after dry and lithium carbonate, Mg (OH)
2and La
2o
3prepare burden, the mol ratio of wherein controlling Li:Co is that the doping of 1.10, Mg and La is respectively 0.1wt% and 0.1wt%;
(3) high temperature solid-phase sintering: the compound obtaining in step (2) is placed in to pushed bat kiln and carries out high temperature solid-phase sintering, sintering temperature is 1000 ℃, and sintering time is 12h, obtains cobalt acid lithium matrix;
(4) coated high-temperature process: after the cobalt acid lithium matrix obtaining in step (3) is pulverized, add the Al of its mass fraction 0.5wt%
2o
3, after high speed mixer mixes, double sintering at 700 ℃ of temperature (i.e. coated high-temperature process), sintering time is 12h, on cobalt acid lithium matrix, forms the uniform metal oxide Al of one deck
2o
3, the product obtaining, with the cooling rear fragmentation of stove, is high voltage lithium cobaltate cathode material.
The median particle diameter D of the anode material for lithium-ion batteries high voltage cobalt acid lithium that after testing, the preparation method of the present embodiment obtains
50be 19 μ m, tap density reaches 3.0g/cm
3, compacted density can reach 4.4g/cm
3; As shown in Figure 2, in the scope of 2.8V～4.35V, the 1C gram volume that discharges first reaches 164mAh/g, and within 300 weeks, circulation volume conservation rate is 92%.
Claims (10)
1. prepare a preprocess method for cobaltosic oxide for high voltage cobalt acid lithium, comprise the following steps:
(1.1) take titaniferous organic substance introduces source as titanium ion, makes itself and immiscible organic solvent, forms the titaniferous organic substance mixed liquor of clarification;
(1.2) under stirring condition, cobaltosic oxide powder is added in described titaniferous organic substance mixed liquor, form suspension-turbid liquid, and continue stirring until evenly;
(1.3) in above-mentioned suspension-turbid liquid, add deionized water, until form milky suspension-turbid liquid, then be stirred well to the even pulpous state fluid foods of formation, then dry, complete coated preliminary treatment, obtain cobaltosic oxide compound.
2. preprocess method according to claim 1, it is characterized in that: described titaniferous organic substance comprises one or more in butyl titanate, tetraethyl titanate, tetraisopropyl titanate, metatitanic acid n-propyl, in described suspension-turbid liquid, to account for the percentage of cobaltosic oxide and the organic gross mass of titaniferous be 0.1wt%～10wt% to titaniferous organic substance.
3. preprocess method according to claim 1, is characterized in that: described organic solvent is methyl alcohol, ethanol or isopropyl alcohol, and the volume ratio of described titaniferous organic substance and organic solvent is controlled as 1:1～1:100.
4. according to the preprocess method described in claim 1,2 or 3, it is characterized in that: in described step (1.2), the lasting mixing time forming after suspension-turbid liquid is controlled as 15min～150min; In described step (1.3), being stirred well to and forming the required mixing time of even pulpous state fluid foods is 15min～150min.
5. according to the preprocess method described in claim 1,2 or 3, it is characterized in that: in described step (1.3), the volume ratio of the titaniferous organic substance mixed liquor of sneaking in the deionized water adding and suspension-turbid liquid is controlled at (0.5～1): (1～10).
6. a preparation method for lithium ion anode material high voltage cobalt acid lithium, comprises the following steps:
(1) batching is mixed: cobaltosic oxide compound, lithium source and alloy that preprocess method described in any one in claim 1～5 is obtained are fully mixed to get compound;
(2) high temperature solid-phase sintering: gained compound is carried out to high temperature solid-phase sintering, obtain cobalt acid lithium matrix;
(3) coated high-temperature process: carry out high-temperature process and make cobalt acid lithium matrix outer cladding form layer of metal oxide on the cobalt acid lithium matrix of gained, obtain high voltage cobalt acid lithium.
7. preparation method according to claim 6, is characterized in that: in described step (1), lithium source comprises one or more in lithium hydroxide, lithium carbonate, lithium oxalate, and the mol ratio of wherein controlling Li: Co is 0.95～1.2; Described alloy comprises oxide, hydroxide or the meta-aluminate of doped chemical, and doped chemical comprises one or more in Mg, Ti, Zr, Al, La; The doping of doped chemical is 0.1wt%～2wt%.
8. preparation method according to claim 6, is characterized in that: in described step (2), the sintering temperature of high temperature solid-phase sintering is controlled at 900 ℃～1500 ℃, and sintering time is controlled as 5h～25h.
9. according to the preparation method described in claim 6,7 or 8, it is characterized in that: in described step (3), described metal oxide is the oxide of one or more elements in Mg, Ti, Zr, Al, La; The covering amount of described metal oxide is 0.1wt%～1wt%; The treatment temperature of coated high-temperature process is 500 ℃～1000 ℃, and the processing time is 5h～25h.
10. the lithium ion anode material high voltage cobalt acid lithium that the preparation method as described in any one in claim 6～9 obtains, is characterized in that, the median particle diameter D of described high voltage cobalt acid lithium
50be 10～20 μ m, tap density is 3.0g/cm
3above, compacted density is at 4.2g/cm
3above, in the scope of 2.8V～4.35V, 1C discharges more than gram volume reaches 164mAh/g first, and within 300 weeks, circulation volume conservation rate is more than 89%.
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| CN106986393A (en) * | 2017-04-28 | 2017-07-28 | 格林美（无锡）能源材料有限公司 | High voltage type cobalt acid lithium and preparation method thereof |
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| CN111924885A (en) * | 2019-05-13 | 2020-11-13 | 天津国安盟固利新材料科技股份有限公司 | Lithium cobaltate positive electrode material and modification method thereof |
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| CN115676902A (en) * | 2021-07-28 | 2023-02-03 | 天津国安盟固利新材料科技股份有限公司 | Al gradient type lithium cobaltate-doped positive electrode material and preparation method thereof |
| CN115676902B (en) * | 2021-07-28 | 2024-05-28 | 天津国安盟固利新材料科技股份有限公司 | Al gradient doped lithium cobalt oxide positive electrode material and preparation method thereof |
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Address after: 410000 Hunan province Changsha Lushan Road No. 966 Co-patentee after: Hunan Changyuan Lithium Co., Ltd. Patentee after: Changsha Research Institute of Mining and Metallurgy Co., Ltd. Address before: 410000 Hunan province Changsha Lushan Road No. 966 Co-patentee before: Hunan Changyuan Lico Co.,Ltd. Patentee before: Changsha Research Institute of Mining and Metallurgy Co., Ltd. |