CN101284681B - Super-size and high-density lithium cobalt oxide and method for preparing the same - Google Patents
Super-size and high-density lithium cobalt oxide and method for preparing the same Download PDFInfo
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- CN101284681B CN101284681B CN2007100653402A CN200710065340A CN101284681B CN 101284681 B CN101284681 B CN 101284681B CN 2007100653402 A CN2007100653402 A CN 2007100653402A CN 200710065340 A CN200710065340 A CN 200710065340A CN 101284681 B CN101284681 B CN 101284681B
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- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 50
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 8
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 33
- 239000010941 cobalt Substances 0.000 claims description 33
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 33
- 239000002253 acid Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 230000035939 shock Effects 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910009951 LiaCo1−bMbO2 Inorganic materials 0.000 abstract 1
- 239000013543 active substance Substances 0.000 abstract 1
- 238000009863 impact test Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 20
- 238000009413 insulation Methods 0.000 description 16
- 230000014759 maintenance of location Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 229910000428 cobalt oxide Inorganic materials 0.000 description 7
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 5
- 238000005469 granulation Methods 0.000 description 5
- 230000003179 granulation Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a high-density lithium cobalt oxide power material with a super-large grain diameter, and the preparation method thereof. The method comprises the steps of mixing a cobalt compound, a lithium compound or meanwhile a small amount of doping element compounds; sintering for 3 to 30 hours at the high temperature of 950 to 1,100 DEG C to form a block sintered product; crushingand grading the product to obtain the lithium cobalt oxide power material (molecular formula is LiaCo1-bMbO2), wherein, when b is not equal to 0, the middle diameter of the lithium cobalt oxide containing the doping elements is larger than or equal to 15 Mum, and the tap density is higher than or equal to 2.5g/cm<3>; when b is equal to 0, the middle diameter of the lithium cobalt oxide without the doping elements is larger than 20 Mum, and the tap density is higher than or equal to 2.6g/cm<3>. The 3.6V platform capacity rate of the material as the anode active substance for a lithium battery is higher than or equal to 75%; in the thermal impact test in a thermotank at 150 DEG C, the lithium battery with the material is free from leakage and does not catch fire or explode for 60 minutes; and the 1C5A specific capacity of the material in the battery is larger than or equal to 135mAh/g.
Description
Technical field
The invention belongs to the technical field of high capacity power source material,, can significantly improve the super-size of the safety performance of lithium ion battery and energy density and high-density lithium cobalt oxide powder body material and preparation method thereof particularly as anode material for lithium-ion batteries.
Background technology
Lithium ion battery is a kind of advanced person's a high energy secondary power supply, has replaced traditional NI-G and nickel-hydrogen secondary cell at present, becomes the driving power of portable electronics such as mobile telephone, notebook computer, field camera, DVD, PDA, MP3.Up to now, cobalt acid lithium obtains extensive industrialized and uses by advantages such as its heavy body, high-voltage, long lifetime, discharge platform are steady in lithium ion battery production.Existing cobalt acid lithium material can satisfy the needs that the lower volume small battery is used on the market, but the lithium ion battery of preparation high-energy, high security is remained in big gap, has limited the raising of battery over-all properties.
Some patents of invention have related to the preparation of cobalt acid lithium material both at home and abroad, but few about the report of big particle diameter, high security product.The certain methods complex process of having reported is difficult to obtain industrial applications.
Japanese Patent JP2004131334 (contriver: Awano Hidekazu etc.) provide a kind of rechargeable nonaqueous electrolytic battery cobalt acid lithium and preparation method thereof.This invention is adopted lithium compound, is heated to 500 ℃ of cobalt compounds that can discharge 0.1～5wt% ammonia is raw material, burns till at 1020 ℃ behind the batch mixing, and the product median size of preparing is 12～13 μ m.
U.S. Pat 20040213729A1 (contriver: Manabu Suhara etc.) provide a kind of cathode plate for lithium secondary battery cobalt acid lithium preparation technology.This patent proposes to consist of Li
pCo
xM
yO
zF
aThe lithium cobalt composite oxide is as positive electrode material, and wherein M is the elements such as other transition metal, aluminium or alkaline-earth metal that are different from Co, 0.9≤p≤1.1,0.980≤x≤1.000,0≤y≤0.02,1.9≤z≤2.1, x+y=1,0≤a≤0.02.The mixture in cobalt source, lithium source, M source, fluorine source etc. under logical oxygen atmosphere, is burnt till in 800～1050 ℃.The cobalt source is that specific surface area is 5～50m
28～20 μ m cobaltous hydroxide coacervates that/g, second particle constitute.This patented technology is owing to adopted macrobead cobalt source, and is more complete for making reaction, adopt under the oxygen atmosphere and burn till, and product is tap density≤2.2 gram/cubic centimetres, D
50Aggregate powder of AI/Yt (D about=11～18 μ m
50Represent meso-position radius, refer to that the cumulative particle sizes percentile of a sample reaches 50% o'clock pairing particle diameter, particle diameter, median size in also claiming).In addition, owing to need to continue logical oxygen, the control difficulty is big, and manufacturing cost is increased.
The preparation method that Chinese patent CN1361061A (contriver: Wu Mengtao, Wang Ruizhong, Zhang Hongwei etc.) has invented cobalt-lithium oxide material, any or its mixture in Quilonum Retard or lithium hydroxide and tricobalt tetroxide, cobalt sesquioxide, the cobaltous carbonate is mixed mutually, and wherein the mole ratio of the former with the latter add-on is 0.95～1.15:1; Above-mentioned compound pine dress is piled up, and its thickness carries out the compressing tablet granulation less than 30 millimeters, and the raw material after granulation carries out high temperature solid state reaction again; The cooling back is pulverized and is got final product.The preparation method of this invention makes the tap density of product obviously be better than cobalt-lithium oxide material without granulation, and its tap density reaches 2.4～2.75 gram/cubic centimetres.The crucial part of this patent is to utilize the pressure of press at 0.5～30MPa, with the granulation of mixed powder compressing tablet, contacts sintering effect between the raising material particles.This technology utilization press apparatus, complex process, and the product meso-position radius is 5～20 μ m.
Chinese patent CN1328351A (contriver: Zhou Henghui, poplar just, Ren Xianju) has invented a kind of meso-position radius of cobalt acid lithium and method of tap density of improving, with Li
2CO
3, LiOH or both mixtures, CoCO
3, Co
3O
4Perhaps both mixtures, LiCoO
2, three kinds of materials mix in proportion; 300～1000 ℃ of following Synthetic 2～20 hour; With the aggregate fragmentation in the synthetic material.Prepared in this way LiCoO
2Meso-position radius and tap density big (being respectively 10～14 μ m, 2.6～2.75 gram/cubic centimetres), and solved once-firing LiCoO
2Macroparticle the particle internal-response that may cause not exclusively and the imperfect problem of crystal formation, avoiding is raising LiCoO
2Meso-position radius and tap density and with LiCoO
2The repeatedly excessive volatilization of the lithium that causes of sintering and to the destruction of particle surface, and energy consumption is huge.But the meso-position radius of this handicraft product has only about 10～14 μ m, and part cobalt acid lithium (0～100%) circulates repeatedly as nucleus, complex process, and production efficiency is low.
From the existing patent documentation that retrieves, do not see meso-position radius〉20 μ m, tap density 〉=2.6g/cm
3Cobalt acid lithium or meso-position radius 〉=15 μ m, tap density 〉=2.5g/cm
3The invention report of doping cobalt acid lithium.
Summary of the invention
One of purpose of the present invention provides a kind of super-size and highdensity cobalt acid lithium product with high security, to overcome the deficiency of prior art; Corresponding product has characteristics such as granularity super large, density height, volume and capacity ratio height, safety performance be good.
Two of purpose of the present invention provides the preparation method of a kind of super-size and high-density lithium cobalt oxide, makes every effort to that technology is simple, cost reduces.
The molecular formula of super-size of the present invention and high-density lithium cobalt oxide is Li
aCo
1-bM
bO
2, wherein, the meso-position radius that does not contain the cobalt acid lithium of doped element during b=0 is〉and 20 μ m, tap density is 〉=2.6g/cm
3The meso-position radius of preferred cobalt acid lithium is 20＜D
50≤ 40 μ m, tap density is 2.6～3.2g/cm
3The meso-position radius that the cobalt acid lithium of doped element o'clock is contained in b ≠ 0 is 〉=15 μ m, and tap density is 〉=2.5g/cm
3The meso-position radius of preferred cobalt acid lithium is 15≤D
50≤ 40 μ m; Tap density is 2.5～3.2g/cm
33.6V platform capacity rate 〉=75% of the lithium ion battery of making as positive active material with this material, the thermal shock test result in 150 ℃ of hot casees be do not leak in 60 minutes, not on fire, do not explode the 1C of material
5A specific storage 〉=135mAh/g.
0.95≤a≤1.20 wherein; 0≤b≤0.20; Doped element M is selected from one or more the element among Ni, Mn, Cr, Fe, Mg, Ca, Sr, Ba, B, Al, Y, Sm, Ti, Zn, Zr, Hf, V, Nb, the Ta; M is raw materials used to be oxide compound, oxyhydroxide, carbonate or the oxalate of above-mentioned doped element, and the cobalt acid lithium that contains doped element is a doping cobalt acid lithium.
Preparation technology's principle of super-size of the present invention and high-density lithium cobalt oxide: cobalt compound, lithium compound are mixed by a certain percentage, or mix by a certain percentage with a small amount of doping element compound simultaneously, making the mol ratio of Li/ (Co+M) is 1.05～1.20, be rapidly heated with 3～20 ℃/minute, through 950～1100 ℃ of high temperature sinterings 3～30 hours, in specific high lithium proportioning, be rapidly heated, under the high temperature sintering condition, make raw material and product generation Partial Liquid Phase molten sintering, generate the macrobead sintered product; Slowly after the cooling, crush and screen again and obtain finished product.
The preparation method of super-size of the present invention and high-density lithium cobalt oxide may further comprise the steps:
(1). mixing material:
Cobalt compound, lithium compound and doping element compound poured in the blender mix, making the mol ratio of Li/ (Co+M) is 1.05～1.20, and the mol ratio of M/ (Co+M) is 0～0.20;
Described M is a doped element, and its source is one or more the mixture in the oxide compound, oxyhydroxide, carbonate, oxalate that contain Ni, Mn, Cr, Fe, Mg, Ca, Sr, Ba, B, Al, Y, Sm, Ti, Zn, Zr, Hf, V, Nb or Ta;
(2). calcining:
The material that step (1) is mixed places calcining vessel (such as but not limited to ceramic saggar, crucible etc.) compacting; Place High Temperature Furnaces Heating Apparatus then, be rapidly heated, temperature rise rate is 3～20 ℃/minute; And, obtain the cobalt acid lithium block materials of black naturally after the cooling in 950～1100 ℃ of high temperature sinterings 3～30 hours.
(3). the broken pulverizing:
The agglomerate that step (2) obtains is pulverized, sieved through broken, obtain final product after the classification.
Step (1) is described to be 1～10 hour with cobalt compound, lithium compound and doping element compound mixing time.
Described lithium compound is Quilonum Retard, lithium hydroxide or both mixtures.
Described cobalt compound is one or more the mixture in the oxide compound, oxyhydroxide, carbonate, oxalate of cobalt.
Super-size of the present invention is compared with the technology of having reported with high-density lithium cobalt oxide, and following advantage is arranged:
1) the cobalt acid lithium particle diameter that adopts the inventive method to obtain is big, and meso-position radius is 15≤D
50≤ 40 μ m, tap density height (〉 2.6g/cm
3), good processability, safety performance be good;
2) unadulterated cobalt acid lithium and adopted the processing characteristics and the chemical property of modification cobalt acid lithium of a small amount of doped element (M) compound better;
3) directly calcine in air, need not to be full of special oxygen atmosphere, cost reduces;
4) adopt the compacting charging method, do not need granulation, can realize contact and sintering between the mixture particle;
5) flow process is short, the technology simple controllable.
Super-size of the present invention and high-density lithium cobalt oxide (as shown in Figure 1), in characteristics such as the high-voltage of inheriting existing cobalt acid lithium material, heavy body, good cycle, have bigger volume energy density, better workability and higher security (as shown in Figure 2), therefore have broad application prospects.
Description of drawings
Fig. 1. Electronic Speculum (SEM) photo of the super-size that contains doped element of the embodiment of the invention 4 and high-density lithium cobalt oxide.
Fig. 2. differential scanning calorimetry (DSC) the result contrast of the super-size that contains doped element of the embodiment of the invention 4 and high-density lithium cobalt oxide and 6um cobalt acid lithium.
Embodiment
Embodiment 1
Take by weighing Quilonum Retard, cobalt oxide, pour thorough mixing in the mixing tank successively into, the mol ratio of control Li/Co is 1.05.Batch mixing is packed in the ceramic saggar after the compacting, place High Temperature Furnaces Heating Apparatus, 10 ℃/min heated up, 980 ℃ of insulations 5 hours.The block materials that obtains black after the cooling is through grinding, after 300 mesh sieves.The meso-position radius of this product is 21.35 μ m, tap density 2.75g/cm
3
This material and carbon black, polyvinylidene difluoride (PVDF) (PVDF) are become pole piece by 94%:3%:3% weight ratio batching and slurry, and negative pole adopts synthetic graphite, the centre add membrane coil around and fluid injection after, be processed into 053048 shell with square aluminum battery; The chemical property of test battery and safety performance.The specific storage of material is 138mAh/g in the battery, and the 3.6V platform capacity rate of battery is 78%, 1C
5Thermal shock test result in 93.5%, 150 ℃ of hot case of 100 capability retentions of A charge and discharge cycles was not exploded in 60 minutes.(according to lithium ion standard GB/T18287-2000:C
5Be rated capacity, expression with 5 hourly rates be discharged to final voltage the electric weight that should provide, unit is Ah or mAh; 1C
5The A charge and discharge cycles is meant under 20 ± 5 ℃ of conditions, with 1C
5A charges to 4.2V, changes constant voltage charge to charging current≤0.01C
5A is again with 1C
5A is discharged to 2.75V, forms 1 cycle, repeats 1C afterwards again
5A charge/discharge process).
Take by weighing Quilonum Retard, cobaltous carbonate, pour thorough mixing in the mixing tank successively into, the mol ratio of control Li/Co is 1.15.Batch mixing is packed in the ceramic saggar after the compacting, place High Temperature Furnaces Heating Apparatus, 15 ℃/min heated up, 1050 ℃ of insulations 5 hours.The block materials that obtains black after the cooling is through grinding, after 300 mesh sieves.The meso-position radius of this product is 37.35 μ m, tap density 2.81g/cm
3
This material is processed into 053048 battery by embodiment 1 same procedure, the chemical property of test battery and safety performance.The specific storage of material is 136mAh/g in the battery, and battery 3.6V platform capacity rate is 76%, 100 1C
5Thermal shock test result in 92.5%, 150 ℃ of hot case of A charge and discharge cycles capability retention was not exploded in 60 minutes.
Take by weighing lithium hydroxide, cobalt oxide, barium carbonate, pour thorough mixing in the mixing tank successively into, the mol ratio of control Li/ (Co+Ba) is 1.05, and the mol ratio of Ba/ (Co+Ba) is 0.05.Batch mixing is packed in the ceramic saggar after the compacting, place High Temperature Furnaces Heating Apparatus, 10 ℃/min heated up, 1080 ℃ of insulations 5 hours.Obtain the black block materials after the cooling through grinding, obtain product behind 300 mesh sieves excessively.The meso-position radius of this product is 27.43 μ m, tap density 2.86g/cm
3
This material is processed into 053048 battery by embodiment 1 same procedure, the chemical property of test battery and safety performance.The specific storage of material is 136mAh/g in the battery, and the 3.6V platform capacity rate of battery is 78%, 100 1C
5Thermal shock test result in 91.3%, 150 ℃ of hot case of A charge and discharge cycles capability retention was not exploded in 60 minutes.
Take by weighing Quilonum Retard, cobalt oxide, aluminum oxide, pour thorough mixing in the mixing tank successively into, the mol ratio of control Li/ (Co+Al) is 1.10, and the mol ratio of Al/ (Co+Al) is 0.05.Batch mixing is packed in the ceramic saggar after the compacting, place High Temperature Furnaces Heating Apparatus, 6 ℃/min heated up, 980 ℃ of insulations 5 hours.The block materials that obtains black after the cooling is through grinding, after 300 mesh sieves.The meso-position radius of this product is 23.32 μ m, tap density 2.78g/cm
3
This material is processed into 053048 battery by embodiment 1 same procedure, the chemical property of test battery and safety performance.The specific storage of material is 135mAh/g in the battery, and battery 3.6V platform capacity rate is 80%, 100 1C
5Thermal shock test result in 91.6%, 150 ℃ of hot case of A charge and discharge cycles capability retention was not exploded in 60 minutes.Contain doped element super-size and high-density lithium cobalt oxide Electronic Speculum (SEM) photo as shown in Figure 1, differential scanning calorimetry (DSC) the result contrast that contains the super-size of doped element and high-density lithium cobalt oxide and 6um cobalt acid lithium is as shown in Figure 2.
Take by weighing Quilonum Retard, cobalt oxide, zirconium white, pour thorough mixing in the mixing tank successively into, the mol ratio of control Li/ (Co+Zr) is 1.05, and the mol ratio of Zr/ (Co+Zr) is 0.01.Batch mixing is packed in the ceramic saggar after the compacting, place High Temperature Furnaces Heating Apparatus, 10 ℃/min heated up, 1080 ℃ of insulations 5 hours.The block materials that obtains black after the cooling is through grinding, after 300 mesh sieves.The meso-position radius of this product is 28.45 μ m, tap density 2.75g/cm
3
This material is processed into 053048 battery by embodiment 1 same procedure, the chemical property of test battery and safety performance.The specific storage of material is 140mAh/g in the battery, and battery 3.6V platform capacity rate is 82%, 100 1C
5Thermal shock test result in 94.5%, 150 ℃ of hot case of A charge and discharge cycles capability retention was not exploded in 60 minutes.
Comparative example 1
Take by weighing Quilonum Retard, cobalt oxide, pour thorough mixing in the mixing tank successively into, the mol ratio of control Li/Co is 1.05.The batch mixing loosely is packed in the ceramic saggar, place High Temperature Furnaces Heating Apparatus, 10 ℃/min heated up, 980 ℃ of insulations 5 hours.Naturally obtain the black block materials after the cooling, through grinding, after 300 mesh sieves.The meso-position radius of this product is 14.26 μ m, tap density 2.45g/cm
3
This material is processed into 053048 battery by embodiment 1 same procedure, the chemical property of test battery and safety performance.The specific storage of material is 138mAh/g in the battery, and battery 3.6V platform capacity rate is 78%, 100 1C
5Thermal shock test result in 93.4%, 150 ℃ of hot case of A charge and discharge cycles capability retention blasted in 24 minutes.
Comparative example 2
Take by weighing Quilonum Retard, cobalt oxide, pour thorough mixing in the mixing tank successively into, the mol ratio of control Li/Co is 1.05.Batch mixing is packed in the ceramic saggar after the compacting, place High Temperature Furnaces Heating Apparatus, 2 ℃/min heated up, 980 ℃ of insulations 5 hours.Naturally obtain the black block materials after the cooling, through grinding, after 300 mesh sieves.The meso-position radius of this product is 19.34 μ m, tap density 2.53g/cm
3
This material is processed into 053048 battery by embodiment 1 same procedure, the chemical property of test battery and safety performance.The specific storage of material is 138mAh/g in the battery, and battery 3.6V platform capacity rate is 77%, 100 1C
5Thermal shock test result in 93.1%, 150 ℃ of hot case of A charge and discharge cycles capability retention blasted in 45 minutes.
Comparative example 3
Take by weighing Quilonum Retard, cobalt oxide, pour thorough mixing in the mixing tank successively into, the mol ratio of control Li/Co is 1.08.Batch mixing is packed in the ceramic saggar after the compacting, place High Temperature Furnaces Heating Apparatus, 10 ℃/min heated up, 700 ℃ of insulations 5 hours.Naturally obtain the black block materials after the cooling, through grinding, after 300 mesh sieves.The meso-position radius of this product is 7.56 μ m, tap density 2.25g/cm
3
This material is processed into 053048 battery by embodiment 1 same procedure, the chemical property of test battery and safety performance.The specific storage of material is 138mAh/g in the battery, and battery 3.6V platform capacity rate is 78%, 100 1C
5Thermal shock test result in 91.3%, 150 ℃ of hot case of A charge and discharge cycles capability retention blasted in 15 minutes.
Embodiment and comparative example result gather
| Project | D 50/μm | Tap density | Specific storage | 3.6 |
100 capability retentions | Thermal shock test | Remarks |
| Embodiment 1 | 21.35 | 2.75 | 138 | 78％ | 93.5％ | OK | Non-impurity-doped, 1.05 proportionings, 10 ℃/min heat up, 980 ℃ of insulations, compacting |
| |
37.35 | 2.81 | 136 | 76％ | 92.5％ | OK | Non-impurity-doped, 1.15 proportionings, 15 ℃/min heat up, 1050 ℃ of insulations, compacting |
| |
27.43 | 2.86 | 136 | 78％ | 91.3％ | OK | Doping, 1.05 proportionings, 10 ℃/min heat up, 1080 ℃ of insulations, compacting |
| |
23.32 | 2.78 | 135 | 80％ | 91.6％ | OK | Doping, 1.10 proportionings, 6 ℃/min heat up, 980 ℃ of insulations, compacting |
| Project | D 50/μm | Tap density | Specific storage | 3.6 |
100 capability retentions | Thermal shock | Remarks |
| Embodiment | |||||||
| 5 | 28.45 | 2.75 | 140 | 82％ | 94.5％ | OK | Doping, 1.05 proportionings, 10 ℃/min heat up, 1080 ℃ of insulations, compacting |
| Comparative example 1 | 14.26 | 2.45 | 138 | 78％ | 93.4％ | Blast in 24 minutes | Non-impurity-doped, 1.05 proportionings, 10 ℃/min heat up, 980 ℃ of insulations, pines are adorned |
| Comparative example 2 | 19.34 | 2.53 | 138 | 77％ | 93.1％ | Blast in 45 minutes | Non-impurity-doped, 1.05 proportionings, 3 ℃/min heat up, 980 ℃ of insulations, compacting |
| Comparative example 3 | 7.56 | 2.25 | 138 | 78％ | 91.3％ | Blast in 15 minutes | Non-impurity-doped, 1.08 proportionings, 10 ℃/min heat up, 700 ℃ of insulations, compacting |
*OK represent by 60 minutes the test, do not leak, not on fire, do not explode.
More as can be seen, adopt high lithium proportioning, compacting charging, be rapidly heated according to last table, and soak, can prepare oversize granule, the sour lithium of cobalt highdensity, high security and doping cobalt acid lithium material.These materials have high voltage, excellent cycle performance and safety performance.
Claims (6)
1. super-size and high-density lithium cobalt oxide, it is characterized in that: the molecular formula of described super-size and high-density lithium cobalt oxide is Li
aCo
1-bM
bO
2, wherein, the meso-position radius that the cobalt acid lithium of doped element o'clock is contained in b ≠ 0 is 〉=15 μ m, tap density is 〉=2.5g/cm
3
0.95≤a≤1.20 wherein; 0＜b≤0.20; Doped element M is selected from more than one the element among Ni, Mn, Cr, Fe, Mg, Ca, Sr, Ba, B, Al, Y, Sm, Ti, Zn, Zr, Hf, V, Nb, the Ta.
2. super-size according to claim 1 and high-density lithium cobalt oxide is characterized in that: the described meso-position radius that contains the cobalt acid lithium of doped element is 15≤D
50≤ 40 μ m; Tap density is 2.5～3.2g/cm
3
3. super-size according to claim 1 and 2 and high-density lithium cobalt oxide, it is characterized in that: 3.6V platform capacity rate 〉=75% of the lithium ion battery of making as positive active material with described super-size and high-density lithium cobalt oxide material, thermal shock test result in 150 ℃ of hot casees be do not leak in 60 minutes, not on fire, do not explode the 1C of material
5A specific storage 〉=135mAh/g.
4. preparation method according to each described super-size of claim 1～3 and high-density lithium cobalt oxide is characterized in that this method may further comprise the steps:
(1). mixing material:
Cobalt compound, lithium compound and doping element compound poured in the blender mix, making the mol ratio of Li/ (Co+M) is 1.05～1.20, mol ratio≤0.20 of 0＜M/ (Co+M);
Described M is a doped element, and its source is one or more the mixture in the oxide compound, oxyhydroxide, carbonate, oxalate that contain Ni, Mn, Cr, Fe, Mg, Ca, Sr, Ba, B, Al, Y, Sm, Ti, Zn, Zr, Hf, V, Nb or Ta;
(2). calcining:
The material that step (1) is mixed places the calcining vessel compacting; Place High Temperature Furnaces Heating Apparatus then, be rapidly heated, temperature rise rate is 3～20 ℃/minute; And, obtain the cobalt acid lithium block materials of black after the cooling in 950～1100 ℃ of high temperature sinterings 3～30 hours;
(3). the broken pulverizing:
The agglomerate that step (2) obtains is pulverized, sieved through broken, obtain final product after the classification.
5. method according to claim 4 is characterized in that: described lithium compound is Quilonum Retard, lithium hydroxide or both mixtures.
6. method according to claim 4 is characterized in that: described cobalt compound is one or more the mixture in the oxide compound, oxyhydroxide, carbonate, oxalate of cobalt.
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