CN103618080B - Prepare the preprocess method, high voltage lithium cobalt oxide anode and preparation method thereof of high voltage cobalt acid lithium cobaltosic oxide - Google Patents
Prepare the preprocess method, high voltage lithium cobalt oxide anode and preparation method thereof of high voltage cobalt acid lithium cobaltosic oxide Download PDFInfo
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- H—ELECTRICITY
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a kind of preprocess method of cobaltosic oxide, comprising: first make titaniferous organic substance and immiscible organic solvent obtain mixed liquor; Under agitation cobaltosic oxide powder is added in mixed liquor and form suspension-turbid liquid, in suspension-turbid liquid, add deionized water, then be stirred well to the even pulpous state fluid foods of formation, dry, obtain cobaltosic oxide compound.The cobaltosic oxide compound of acquisition, lithium source and alloy are fully mixed, carries out high temperature solid-phase sintering and coated high-temperature process, namely obtain high voltage cobalt acid lithium.The high voltage cobalt acid lithium that the present invention obtains, its tap density reaches 3.0g/cm
3above, compacted density is at 4.2g/cm
3above, in the scope of 2.8V ~ 4.35V, the 1C gram volume that discharges first reaches more than 164mAh/g, and within 300 weeks, circulation volume conservation rate is more than 89%, has that good processability, tap density are high, good cycle, specific capacity advantages of higher.
Description
Technical field
The invention belongs to the preparing technical field of new forms of energy conversion and storing technology and Related product, particularly relate 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 grown up the nineties in 20th century, because of plurality of advantages such as volume are little, lightweight, specific energy large, be easy to carry, portable type electronic product and Move tool obtains extensive use.
Cobalt acid lithium has many advantages do not replaced as the commercial anode material for lithium-ion batteries of the first generation: such as operating voltage higher (average working voltage is 3.7V), charging/discharging voltage is steady, specific energy is high, good cycle, conductivity is high, and production technology is simple, easily preparation etc., can say, cobalt acid lithium is the most ripe, that the commercialization time is the longest anode material for lithium-ion batteries now.But, due to factors such as microstructures, Li
1-xcoO
2deintercalation coefficient must meet x≤0.5, otherwise too much lithium deintercalation can make material internal structure cave in, 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 gram volume actual at present plays only has 140mAh/g ~ 150mAh/g.
Along with further miniaturization and the multifunction of the portable electronics such as mobile phone, notebook computer, video camera, requirement battery being exported to energy density is more and more higher, conventional cobalt acid lithium can not meet the requirement of the volume capacity density improved constantly, research finds, the charging voltage and then the raising lithium ion battery volume energy density that improve positive electrode become a kind of effective way.The discharge and recharge of existing lithium ion battery is interval basic between 3.0V ~ 4.2V, and with the cobalt acid lithium lithium ion cell charging that is positive electrode to the capacity that can increase about 14.0% during 4.4V, but its cyclical stability of lithium ion battery, thermal stability and the security performance under 4.4V high voltage all can obviously decline.Therefore, the key technical problem that cobalt acid lithium stability under high voltages becomes this area needs solution how is improved.
CN1697212A Chinese patent literature and US6555269B2 american documentation literature all mention 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 electrochemicalproperties of coating ZrO
2on LiCoO
2" .Journal of Alloys and Compounds, 496 (2010) 512-516) and in coated zirconia is also proposed after improve cobalt acid lithium high temperature charge-discharge performance.The CN101872859A Chinese patent literature employing liquid-phase hydrolysis precipitation method make the Ti in solution
4+or Zr
4+precipitation, to the surface of cobalt acid lithium, realizes the coated of cobalt acid lithium, improves the cycle characteristics of material and anti-overshoot characteristics.In the patent documentation delivered at present, mainly concentrate on employing adulterate to cobalt acid lithium and carry out coated method raising material combination property under high voltages to finished product cobalt acid lithium, but it is less with the report realizing material stability under high voltages first to carry out preliminary treatment to raw material.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, a kind of preprocess method that can be used for the cobaltosic oxide of the lithium ion anode material high voltage cobalt acid lithium of 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 the lithium ion anode material high voltage cobalt acid that a kind of good processability, tap density are high, good cycle, specific capacity are high lithium.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of preprocess method preparing high voltage cobalt acid lithium cobaltosic oxide, comprises the following steps:
(1.1) with titaniferous organic substance for titanium ion introduces source, make itself and immiscible organic solvent, formed clarification titaniferous organic substance mixed liquor;
(1.2) under agitation 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, deionized water is added, until form milky suspension-turbid liquid, be stirred well to again and form even pulpous state fluid foods, then carry out drying (such as can preferably dry in the mixing equipment of drying function), complete coated preliminary treatment, obtain cobaltosic oxide compound.
In above-mentioned preprocess method, preferably, 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 preferably controls as 1:1 ~ 1:100.
In above-mentioned preprocess method, preferably, in described step (1.2), the Keep agitation time controling formed after suspension-turbid liquid is 15min ~ 150min.
In above-mentioned preprocess method, preferably, in described step (1.3), being stirred well to the mixing time formed needed for even pulpous state fluid foods is 15min ~ 150min.
In above-mentioned preprocess method, preferably, in described step (1.3), the volume ratio of the titaniferous organic substance mixed liquor be mixed in the deionized water added and suspension-turbid liquid controls in (0.5 ~ 1): (1 ~ 10).
In the technical scheme of the invention described above, by carrying out coated preliminary treatment to raw material cobaltosic oxide, at the uniform titanium-containing compound of cobaltosic oxide Surface coating one deck, titanium elements can be made to enter cobalt acid lithium lattice more equably, and then can stable crystal structure in high-tension situation, caving in of the crystal structure preventing deep discharge from causing.
As a total technical conceive, the present invention also provides the preparation method of a kind of lithium ion anode material high voltage cobalt acid lithium, comprises the following steps:
(1) batching mixing: the cobaltosic oxide compound obtained by above-mentioned preprocess method, lithium source and alloy fully mix, and (general high speed ball milling of selecting mixes) obtains compound;
(2) high temperature solid-phase sintering: gained compound is carried out high temperature solid-phase sintering, obtains 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, preferably, in described step (1), lithium source comprise in lithium hydroxide, lithium carbonate, lithium oxalate one or more, the mol ratio of wherein control Li: Co is 0.95 ~ 1.2; Described alloy comprises the oxide of doped chemical, hydroxide or meta-aluminate, doped chemical comprise in Mg, Ti, Zr, Al, La one or more; The doping of doped chemical refers to the mass fraction shared by all doped chemicals are in sintered products for 0.1wt% ~ 2.0wt%(doping, draws the addition of alloy in preparation process according to can instead push away the design of doping).
In above-mentioned preparation method, preferably, in described step (2), the sintering temperature of high temperature solid-phase sintering controls at 900 DEG C ~ 1500 DEG C, and sintering time controls as 5h ~ 25h.
In above-mentioned preparation method, preferably, in described step (3), described metal oxide is the oxide (being more preferably the oxide of Zr, Al) of one or more elements in Mg, Ti, Zr, Al, La; The covering amount (metal oxide accounts for the quality of cobalt acid lithium matrix) of described metal oxide is 0.1wt% ~ 1wt%.Preferred, in described step (3), the treatment temperature of coated high-temperature process is 500 DEG C ~ 1000 DEG C, and the processing time is 5h ~ 25h.By adding metal oxide in cobalt acid lithium matrix batch mixing process, then carrying out high-temperature process, effectively ensure that the uniformity of metal oxide in the distribution of 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 μm, tap density is 3.0g/cm
3above, compacted density is at 4.2g/cm
3above, in the scope of 2.8V ~ 4.35V, the 1C gram volume that discharges first reaches more than 164mAh/g, and within 300 weeks, circulation volume conservation rate is more than 89%.
The high voltage cobalt acid lithium product of above-mentioned specific median particle diameter, specific density can be obtained by above preparation technology of the present invention, 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 dissolved in the electrolytic solution increases, capacity attenuation is too fast, and compacted density is on the low side; And although granularity is conducive to too greatly improving material compacted density, capacity plays limited, and therefore suitable particle size range ensures that material has the key factor of higher capacity and cycle performance under high-voltage state.
Compared with prior art, the invention has the advantages that:
(1) the present invention is by carrying out preliminary treatment to cobaltosic oxide, effectively improves the uniformity of material, adds the stability of positive electrode crystal structure under high-voltage state.
(2) by controlling material particle size and carrying out coated process to cobalt acid lithium matrix, decrease the dissolving of cobalt acid lithium cobalt under high voltages, ensure that the specific capacity of cobalt acid lithium product under high-voltage state and cycle performance.
(3) the present invention is by the double sintering merging treatment of coated metal oxide and cobalt acid lithium on cobalt acid lithium matrix, and directly propose the implementation step of coated high-temperature process, this not only enhances the covered effect of metal oxide, and effectively reduces the energy consumption of technique.
(4) the high voltage cobalt acid lithium Product processing performance prepared of the inventive method is good, tap density is high, and under the discharge voltage of>=4.3V, have good cycle performance and gram volume, 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, and can realize increasingly automated, waste of raw materials is few, is very applicable to 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 the embodiment of the present invention 1 obtains.
Fig. 2 is the cyclic curve figure of the lithium ion battery adopting the anode material for lithium-ion batteries high voltage cobalt of embodiment of the present invention acid lithium to be made into.
Embodiment
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but protection range not thereby limiting the invention.
Embodiment 1:
A preparation method for high voltage lithium cobalt oxide anode of the present invention, comprises the following steps:
(1) the coated preliminary treatment of cobaltosic oxide: by tetraisopropyl titanate and absolute ethyl alcohol miscible, the volume ratio of tetraisopropyl titanate and absolute ethyl alcohol controls, for 1:10, to form the tetraisopropyl titanate mixed liquor of clarification; Under the state stirred, the powder of cobaltosic oxide is added in tetraisopropyl titanate mixed liquor, form suspension-turbid liquid, and Keep agitation 30min is to even, in suspension-turbid liquid, tetraisopropyl titanate accounts for the percentage of the gross mass of cobaltosic oxide and tetraisopropyl titanate is 0.1wt%; Then in the suspension-turbid liquid after mixing, dropwise deionized water is added, the volume ratio of tetraisopropyl titanate mixed liquor be mixed in the deionized water dripped and suspension-turbid liquid is 1: 1, until after forming even milky suspension-turbid liquid, stir 30min again, then carry out drying, obtain cobaltosic oxide compound for subsequent use;
(2) prepare burden: by the cobaltosic oxide compound that obtains after drying and lithium carbonate, Mg (OH)
2and La
2o
3prepare burden, wherein the mol ratio of control Li:Co is that the doping of 1.06, Mg and La is respectively 0.15wt% and 0.05wt%, can determine Mg (OH) according to this doping
2and La
2o
3addition in batching;
(3) high temperature solid-phase sintering: the compound obtained in step (2) is placed in pushed bat kiln and carries out high temperature solid-phase sintering, sintering temperature is 1000 DEG C, and sintering time is 12h, obtains cobalt acid lithium matrix;
(4) coated high-temperature process: after being pulverized by the cobalt acid lithium matrix obtained in step (3), add the ZrO of its mass fraction 1wt%
2, after high speed mixer mixing, double sintering (i.e. coated high-temperature process) at 800 DEG C of temperature, sintering time is 12h, and cobalt acid lithium matrix forms the uniform metal oxide ZrO of one deck
2, the product obtained, with broken after stove cooling, is high voltage lithium cobalt oxide anode.
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 μm, 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 cobalt oxide anode of the present invention, comprises the following steps:
(1) the coated preliminary treatment of cobaltosic oxide: by tetraisopropyl titanate and absolute ethyl alcohol miscible, the volume ratio of tetraisopropyl titanate and absolute ethyl alcohol controls to be 1: 20, formed clarification tetraisopropyl titanate mixed liquor; Under the state stirred, the powder of cobaltosic oxide is added in tetraisopropyl titanate mixed liquor, form suspension-turbid liquid, and Keep agitation 30min is to even; In suspension-turbid liquid, tetraisopropyl titanate accounts for the percentage of the gross mass of cobaltosic oxide and tetraisopropyl titanate is 0.1wt%; Then in the suspension-turbid liquid after mixing, dropwise deionized water is added, the volume ratio of tetraisopropyl titanate mixed liquor be mixed in the deionized water dripped and suspension-turbid liquid is 1: 1, until after forming even milky suspension-turbid liquid, stir 30min again, then carry out drying, obtain cobaltosic oxide compound for subsequent use;
(2) prepare burden: by the cobaltosic oxide compound that obtains after drying and lithium carbonate, MgO and TiO
2prepare burden, wherein the mol ratio of control 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 obtained in step (2) is placed in pushed bat kiln and carries out high temperature solid-phase sintering, sintering temperature is 1300 DEG C, and sintering time is 12h, obtains cobalt acid lithium matrix;
(4) coated high-temperature process: after being pulverized by the cobalt acid lithium matrix obtained in step (3), add the ZrO of its mass fraction 1wt%
2, after high speed mixer mixing, double sintering (i.e. coated high-temperature process) at 800 DEG C of temperature, sintering time is 12h, and cobalt acid lithium matrix forms the uniform metal oxide ZrO of one deck
2, the product obtained, with broken after stove cooling, is high voltage lithium cobalt oxide anode.
After testing, the median particle diameter D of the anode material for lithium-ion batteries high voltage cobalt acid lithium of preparation method's acquisition of the present embodiment
50be 15 μm, 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 cobalt oxide anode of the present invention, comprises the following steps:
(1) the coated preliminary treatment of cobaltosic oxide: by butyl titanate solution and absolute ethyl alcohol miscible, the volume ratio of butyl titanate and absolute ethyl alcohol controls, for 1:50, to form the butyl titanate mixed liquor of clarification; Under the state stirred, the powder of cobaltosic oxide is added in butyl titanate mixed liquor, form suspension-turbid liquid, and Keep agitation 30min is to even; In suspension-turbid liquid, butyl titanate accounts for the percentage of the gross mass of cobaltosic oxide and butyl titanate is 10wt%; Then in the suspension-turbid liquid after mixing, dropwise deionized water is added, the volume ratio of butyl titanate mixed liquor be mixed in the deionized water dripped and suspension-turbid liquid is 1:1, until after forming even milky suspension-turbid liquid, then stirs 30min, then carry out drying, obtain cobaltosic oxide compound for subsequent use;
(2) prepare burden: by the cobaltosic oxide compound that obtains after drying and lithium carbonate, Mg (OH)
2and La
2o
3prepare burden, wherein the mol ratio of control 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 obtained in step (2) is placed in pushed bat kiln and carries out high temperature solid-phase sintering, sintering temperature is 1000 DEG C, and sintering time is 12h, obtains cobalt acid lithium matrix;
(4) coated high-temperature process: after being pulverized by the cobalt acid lithium matrix obtained in step (3), add the Al of its mass fraction 0.5wt%
2o
3, after high speed mixer mixing, double sintering (i.e. coated high-temperature process) at 700 DEG C of temperature, sintering time is 12h, and cobalt acid lithium matrix forms the uniform metal oxide Al of one deck
2o
3, the product obtained, with broken after stove cooling, is high voltage lithium cobalt oxide anode.
After testing, the median particle diameter D of the anode material for lithium-ion batteries high voltage cobalt acid lithium of preparation method's acquisition of the present embodiment
50be 19 μm, 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 (7)
1. prepare a preprocess method for high voltage cobalt acid lithium cobaltosic oxide, comprise the following steps:
(1.1) with titaniferous organic substance for titanium ion introduces source, make itself and immiscible organic solvent, form the titaniferous organic substance mixed liquor of clarification, the volume ratio of described titaniferous organic substance and organic solvent controls to be 1:1 ~ 1:100;
(1.2) under agitation cobaltosic oxide powder is added in described titaniferous organic substance mixed liquor, form suspension-turbid liquid, and continue stirring until evenly; In described suspension-turbid liquid, titaniferous organic substance accounts for the percentage of cobaltosic oxide and the organic gross mass of titaniferous is 0.1 wt% ~ 10 wt%;
(1.3) in above-mentioned suspension-turbid liquid, deionized water is added, the volume ratio of the titaniferous organic substance mixed liquor be mixed in the deionized water added and suspension-turbid liquid controls in (0.5 ~ 1): (1 ~ 10), until form milky suspension-turbid liquid, be stirred well to again and form even pulpous state fluid foods, then dry, complete coated preliminary treatment, obtain cobaltosic oxide compound.
2. preprocess method according to claim 1, is characterized in that: described titaniferous organic substance comprise in butyl titanate, tetraethyl titanate, tetraisopropyl titanate, metatitanic acid n-propyl one or more.
3. preprocess method according to claim 1, is characterized in that: described organic solvent is methyl alcohol, ethanol or isopropyl alcohol.
4. the preprocess method according to any one of claims 1 to 3, is characterized in that: in described step (1.2), and the Keep agitation time controling formed after suspension-turbid liquid is 15min ~ 150min; In described step (1.3), being stirred well to the mixing time formed needed for even pulpous state fluid foods is 15min ~ 150min.
5. a preparation method for lithium ion anode material high voltage cobalt acid lithium, comprises the following steps:
(1) batching mixing: the cobaltosic oxide compound obtained by preprocess method according to any one of Claims 1 to 4, lithium source and alloy are fully mixed to get compound; Wherein the mol ratio of control Li: Co is 0.95 ~ 1.2, and the doping of doped chemical is 0.1wt % ~ 2wt%;
(2) high temperature solid-phase sintering: gained compound is carried out high temperature solid-phase sintering, the sintering temperature of high temperature solid-phase sintering controls at 900 DEG C ~ 1500 DEG C, and it is 5 h ~ 25 h that sintering time controls, and obtains 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; The treatment temperature of described coated high-temperature process is 500 DEG C ~ 1000 DEG C, and the processing time is 5 h ~ 25 h.
6. preparation method according to claim 5, is characterized in that: in described step (1), lithium source comprise in lithium hydroxide, lithium carbonate, lithium oxalate one or more; Described alloy comprises the oxide of doped chemical, hydroxide or meta-aluminate, doped chemical comprise in Mg, Ti, Zr, Al, La one or more.
7. the preparation method according to claim 5 or 6, is characterized in that: in described step (3), and 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 %.
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| CN104282880B (en) * | 2014-10-24 | 2017-05-17 | 湖南杉杉能源科技股份有限公司 | Lithium-cobalt composite oxide lithium ion positive material and preparation method thereof |
| CN104993148A (en) * | 2015-06-16 | 2015-10-21 | 田东 | Synthesizing method for lithium-ion positive electrode material of LiCoO2/C |
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| CN106986393B (en) * | 2017-04-28 | 2018-09-07 | 格林美（无锡）能源材料有限公司 | High voltage type cobalt acid lithium and preparation method thereof |
| CN111924885B (en) * | 2019-05-13 | 2023-02-17 | 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 |
| CN112744871B (en) * | 2019-10-31 | 2022-12-13 | 天津国安盟固利新材料科技股份有限公司 | Lithium cobaltate cathode material and preparation 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 |
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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. |
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